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- In turn of the century London, a magical nanny employs music and adventure to help two neglected children become closer to their father.
- A computer hacker is abducted into the digital world and forced to participate in gladiatorial games where his only chance of escape is with the help of a heroic security program.
- A wily old codger matches wits with the King of the Leprechauns and helps play matchmaker for his daughter and the strapping lad who has replaced him as caretaker.
- Gilbert Ivy and his wife Jewell are farmers. They seem to be working against the odds, producing no financial surplus. Gilbert has lost hope of ever becoming prosperous, but his wife decides to fight for her family.
- Four months after Vaughn's murder by the traitorous Gordon Dean and his associate Ivan Curtis, a grief-stricken Sydney teams up with Renée Rienne, a French freelance assassin and fugitive on the CIA's most wanted list who knew Vaughn from their past association with Prophet Five, to ask for leads in order to track down the killers before they can strike again. Meanwhile, Jack enlists a reluctant new agent, Thomas Grace, as Vaughn's replacement at APO, and Weiss struggles to decide whether or not to accept a promotion that would force him to move to Washington D.C. and leave his colleagues at APO. During this time, Sydney, Dixon and Weiss travel to Amsterdam to track down Curtis who is in the process of buying a potential weapon.
- Sydney and Dixon are sent on a dangerous case involving the safety of the United Commerce Organization. Francie gets suspicious about Charlie and spies on him. Meanwhile, Will continues to investigate the truth about Danny's murder.
- Nadia's former caretaker, Sophia, has been severely beaten. She contacts Nadia and asks to meet her. Sloane is told by Sophia that she was beaten up, because someone is trying to track Nadia down, so he and Jack decide to tell their daughters the truth. It turns out that Elena Derevko, the third and the cruelest of the Derevko sisters, has been surveying both Sydney and Nadia for a decade. Meanwhile, Jack's doctor advises him to tell Sydney about his illness.
- When Sydney learns that Vaughn is under investigation for being a double agent, Jack and Irina forge an unlikely partnership in their attempt to get their daughter out of the CIA for good. Kendall learns that Sark and Sloane are attempting to get their hands on a Rambaldi manuscript detailing the works of the human heart, so he sends Jack and Irina to Bangkok to learn more, and then to Panama to capture Sloane. But Irina betrays Jack and escapes from custody... this time for real.
- Sydney finally has the opportunity to leave the CIA for good, but a startling phone call from Sloane, combined with the kidnapping of a brilliant mathematician, brings her back into the fray.
- When Sydney learns that Marshall has been kidnapped, she struggles against a heartless Sloane to bring Marshall back whom is being tortured by the same Taiwanese torturer Dr. Lee "Suit and Glasses" to uncover the code for the top secret ECHELON security system whom tries to stall for time. Sydney and Dixon are instead sent to Ho Chi Minh City, Vietnam to recover the hard drive for ECHELON. Meanwhile, Kendall and the rest of the CIA frantically tries to prevent SD-6 from gaining access to ECHELON... and Jack realizes that the only one who can help them is Irina.
- While Nadia is in a coma after being shot by Anna, Sark is taken into APO to help them infiltrate the Cadmus Revolutionary Front and retrieve the stolen bomb, but in return he demands to see Lauren Reed's corpse and that Vaughn open her coffin for him. Sydney learns that the comatose Nadia may be the only person with the Intel they need to intercept the bomb, so Jack is forced to prematurely wake Nadia from her coma, endangering her life, which doesn't please Sloane when he finds out.
- Sydney discovers a link to her missing two years in the form of Simon Walker, the dangerous leader of a group determined on retrieving deadly biological weapons. Meanwhile, Vaughn struggles with his own feelings of jealousy and longing while Sydney is on her mission, aware of the pressures his job is putting on his marriage to Lauren. Jack takes matters into his own hands to protect his daughter, and purposefully revealing Sydney's deadly secret of being a brainwashed assassin for the Covenant during her two-year absence to Dixon in order to preserve her position inside the CIA.
- Sydney and Vaughn are sent to retrieve the Doleac Agenda to gain an advantage over The Covenant. For this, Sydney and Weiss must convince rogue security systems designer Toni Cummings to help the CIA break into a Lethal Response System. Meanwhile, Sark approaches an unlikely ally, that of Lauren Reed, to kill the Covenant's six cell leaders in order to take control of Covenant for themselves.
- Sloane must take a difficult decision in order to get to the Alliance's council. After being captured by Sark, Tippin is tortured by a Taiwanese would-be dentist to extract secrets. Sydney, who has to beware her colleague Dixon, assist her father trying to save Tippin. However, after losing Vaughn when the lab exploded, she is in for a surprise...
- Sydney and Vaughn tell Jack about Sloane's alleged involvement in Vaughn's search for his father and Irina's contract on Sydney's life. After cornering Sloane, they both conclude that someone is framing him. The APO team set a trap to catch the fake A. Sloane, but they fail. Once they realize what "Arvin Clone" is after, Sloane suggests to step down, temporarily. However, Sydney reluctantly convinces him to stay on the case, since he may the only person able to anticipate "Arvin Clone"'s next move. But Nadia fears that this pursuit may revive her father's past obsession: Rambaldi.
- Five months later. Sydney quits the CIA and joins a Black Ops unit called "Authorized Personnel Only" alongside Dixon, Jack, Vaughn and... Sloane whom for limited immunity is co-operating with the APO. Meanwhile, the truth Sydney found out in Wittenberg endangers her relationship with Jack, and eventually she reveals the awful truth to Vaughn: about her father having Irina murdered over a year earlier.
- Sydney unwillingly teams up with her father to hunt down a modern-day samurai, named Kazu Tamazaki. Meanwhile, Nadia is back home in Argentina and refuses to go back into the spy business. But she is forced to when Sydney's life is jeopardized when she's taken captive by the brutal Tamazaki. Sydney finds out the reason behind Jack's misdeed and Nadia makes an unsettling promise to Sydney to find out who murdered Irina.
- Jack, Sydney, Irina, Vaughn and Nadia parachute into Sovogda, Russa to dismantle the giant floating red ball of the Circumfrence which is turning people into mindless, red-eyed zombies out to kill. Back at APO, Marshall and Weiss try use the Blackwell Index to blackmail the Russian defense minister into giving them the access codes to a Russian satellite before the local authorities plan to drop a nuclear bomb on the city to destroy it and prevent the spread of the contagion, and they also discover that Elena is up linking the satellite. In the ruins of the city, a CIA agent, Brodien (the one whom Sydney rescued from Shanghai in the season opener) reminds them that the Rambaldi device is broadcasting a sub audible frequency that physiologically alters people who drink the water-like fluid that has infected the city's water supply and it is irreversible. At the same time, Elena learns of the APO team's arrival and sends Sloane and her men to go out to kill them, leading to a three-way war between Elena's henchman, the APO group, and the zombies leading to Nadia becoming infecting and having a final one-on-one confrontation with Sydney atop a building with the red ball Circumference in the balance.
- After finally discovering the identity of the Rambaldi "Passenger," who is Sloane's illegitimate daughter, Sydney and Jack seek the aid of Sloane, to track the "Passenger" down, first by Sloane meeting with the five key members of a secret government group called "The Trust" to gain access to a Rambaldi device to locate the "Passenger". Sydney then travels to Chechnya to a prison where she finally finds her half-sister, Nadia Santos, an Argentine national and secret agent in hiding. Meanwhile, after learning a secret about his father from Thomas Brill, Vaughn is kidnapped and tortured by Lauren and Sark, who are about to track "The Passenger" down themselves while Dixon, Weiss and Marshall race against the clock to find Vaughn before he is killed.
- While trying to retrieve a bomb, Sydney and Vaughn are ambushed by unidentified assailants. Meanwhile, Lauren and Sark continue to solidify their new partnership as the new leaders of the Covenant. Sloane divulges a dark secret to CIA therapist Dr. Judy Barnett about his past involving Sydney and Irina Derevko. Also, Marshall shows the strains of new fatherhood.
- An incident concerning a microwave bomb brings APO to send Rachel in Sao Paolo in order to take information about this weapon. However, another person who is named "Bob" is also after this information. Rachel has a fling with him, but back at APO, she finds out that he is Julian Sark. Meanwhile, Jack and an old friend are caught by Lazaré while on a stalking mission. Knowing Rachel has a clue to meet Stark, Sydney must deal with this foe in order to free her father from the hands of Lazaré in Tunisia...
- When Sydney is taken into custody by the NSC honcho Mr. Lindsey, Jack and Vaughn have no choice but to ally themselves with Sloane to rescue her. But with only hours to spare before she is forced to undergo a radical surgery to recover her memories, they must put together an extraction team, headed by freelance operative Brill. Meanwhile, Lauren faces an impossible choice: side with the NSC who she wants to believe is doing the right thing, or with her husband in their rescue of Sydney.
- Sydney must travel to Sri Lanka to outwit Sark in order to find a crucial piece of Intel from a computer disk that she recovers from Rabal. Meanwhile, Jack faces Sydney's mother for the first time in almost 20 years in her prison cell to discuss Sydney's well being. Also, Will finally meets Vaughn, and Sloane is haunted by his wife's death when someone begins sending him anonymous letters which have Emily's handwriting on them.
- Trapped in the Romanian asylum run by the Russian spy group, K-Directorate, Sydney befriends amnesiac agent Mark Shephard. Sloane and Alliance representative Alain Christophe come to conclusion that SD-6 has mole(s) and plan a trap.
- After making a shocking discovery of a severed human hand in the desert that belonged to Lazarey, the Russian diplomat she murdered while working as a brainwashed assassin for the Covenant, and who may in fact be alive, Sydney agrees to submit to an experimental procedure conducted by an eccentric doctor, named Dr. Brezzel, designed to retrieve her lost memories. But while Jack and Vaughn look on, Sydney's mind proves surprisingly resistant to letting her remember her missing time... and the process of recovering it could end up killing her. Meanwhile, Lauren makes a great sacrifice of allowing herself to get tortured and beaten up in order to make her alibi believable to Lindsey after helping breaking Sydney out of NSC custody. Also Sloane finds himself boxed in by an unlikely enemy, that of Mr. Lindsey, who wants to see Sydney Bristow eliminated permanently.
- Jack contacts a mysterious woman, that of former KGB agent Katya Derevko, Irina's older sister, to help him free Sydney and Vaughn, whose plane has crashed inside North Korea while seeking to find a defecting Russian scientist, named Leonid Lisenker, whom Sark is trying to kill before turning himself to the CIA. But Jack is faced with a curious conundrum when Katya tells him that she will not put the rescue plan in motion until he fulfills a favor: assassinate Sloane.
- Past demons revisit all the characters as Sloane becomes confused and desperate over clues that his wife may not be dead. At the same time, Will meets a woman who claims to know the truth about SD-6. And Jack tries to convince Sydney that Irina is setting the stage to betray them and will go to any lengths to prove it.
- While Sydney and Nadia argue about Nadia's acceptance of Sloane's fatherly concerns, Sloane worries about Nadia's well-being when she and Sydney go undercover as wealthy, irresponsible young Hilton-type heiresses to uncover the whereabouts of a deadly chemical from a playboy arms dealer.
- Sydney's cover in SD-6 is put in danger after smuggling a wrong biotech engineer into SD-6 from her mission in Berlin. Meanwhile, Will's investigation into Danny's murder leads him to a woman named Kate Jones, who may have information about the killing. Sydney's starts to doubt where her father's true allegiances lie.
- When a young CIA agent dies, suspicion immediately falls on her parter and lover, agent Jim Lennox. But after Sydney rescues Lennox from captivity, She trikes up an instant connection as they discover shared wounds - realizing They've both lost someone they love to the job. Yet even her judgment is thrown when Vaughn and Jack discover that Lennox was pursing a technology that allows people to change their appearance. Now Sydney must ask herself: is this the real Jim Lennox - or is his double?
- Sloane temporarily steps down as director of his APO task force and gives Jack full authority over the next assignment, which involves Anna Espinosa, the former K-Directorate assassin and Sydney's old foe into racing her to go after stolen classified documents. However, Anna turns the tables on APO when she captures Nadia and forces Sydney to do her bidding. During this time, Sydney tells Nadia about the Rambaldi's prophecy which dictates that "two sisters will fight, and only one will survive." Meanwhile, Vaughn visits the imprisoned Sark and tries to trick him into helping them to catch Anna.
- When the CIA intercepts a secret message, Sydney discovers that the life of Neil Caplan, the mathematician still held captive by Sloane and Irina, may be in danger from the most unlikely source: his wife Elsa whom Jack has arrested, forcing Sydney to try to clear Elsa's name by going on her own mission to Moscow and Spain to try to rescue Neil Caplan. Meanwhile, Sloane becomes obsessed with finding out who accidentally killed Emily, and Sark makes contact with the Francie impostor to locate the person responsible... by using Will to infiltrate the CIA satellite surveillance systems.
- Sydney and Vaughn must convince bomb maker Daniel Ryan that they are part of The Covenant in order to find out where he has hidden one of his devices. But Sydney discovers that her ties to the bomber could lead him on a suicide mission when she learns that Ryan's brother was the murder victim that she killed during her interment with the Covenant, and now Ryan wants revenge.
- Sloane decides to betray Dean when he learns that Nadia's condition will probably not improve. They meet at a race track in Dubai to exchange a network access card which Sydney and Renee stole in Rome, leading to Dean finally being captured. The APO interrogates Dean for information on Prophet Five. Yet another mysterious stranger asks Sloane to eliminate Dean. Meanwhile, Nadia comes out of her coma for a short time after a nameless nurse leaves her room. Under orders from his new Prophet Five contacts, Sloane kills Dean during a routine reboot of the APO's surveillance network, and APO misses its chance to hack the network, but learns Prophet Five is linked to intelligence agencies around the world. At the end, control of Dean's terrorist cell is given to Kelly Peyton.
- When Sloane gets his hands on a terrifying Rimbaldi weapon that causes internal spontaneous combustion, Sydney must turn to a betrayed and hurt Dixon for help. But when her ex-partner refuses any assistance, She has no choice but to carry out the mission herself. When Sydney is captured, Vaughn must persuade Dixon to help the CIA rescue Sydney from an Afghan warlord's camp.
- In this episode, Sydney finally learns the shocking truth about her missing two years from an unlikely source: FBI Special Officer Kendall. Kendall whisks her away and talks to her from the privacy of an airborne 757 jet. According to Kendall, Sydney was captured by the Covenant after her fight with Francie/Allison, held captive in Russia for over a year and brainwashed to become an assassin. But Sydney only pretended to be brainwashed and contacted Kendall who became her contact and handler, thus giving him information about the Covenant and about their quest for Rambaldi artifacts. Sydney also staged the murder of Andrian Lazarey, and then deliberately had her memory erased to prevent the Covenant from knowing about secrets she had learned about Rambaldi's findings.
- After finding out that Lauren really is working for the Covenant, Vaughn is told by Jack and Sydney to keep up the facade of a happy marriage in order to keep tabs on his wife's activities. But he's in for a shock when he uncovers the truth about Lauren's mother, Olivia, whom is in league with her daughter over the Covenant's activities. Meanwhile, Jack refuses to help exonerate Sloane of his crimes and put in motion a stay of execution, and a monk discloses the identity of the Rambaldi "Passenger" to Sydney.
- Sydney and Vaughn go undercover to track down a deadly new bio-weapon. Meanwhile, Sydney is concerned about Vaughn not having yet put Lauren behind, and Nadia turns to a Jack to ask for his help in finding out the truth about her mother's murder, who tries to throw Nadia away from the evidence pointing to him.
- Sydney and the rest of the team finally capture the Sloane impostor and bring him to APO where they question him to find a rare Rambaldi orchid whose pollen has some miraculous capabilities with a Rambaldi device. However, the real Sloane must relive a painful memory with his late wife Emily in order to get the Imposter Sloane to reveal the orchid location.
- With the aid of Katya Derevko and CIA imprisoned security systems designer Toni Cummings, Sydney and Vaughn attempt to track down Sloane and Nadia. But Lauren and Sark are also in hot pursuit of them in order to uncover the secrets of Rambaldi. Meanwhile, Vaughn's obsession with tracking down Lauren is beginning to consume him. During a mission to Cuba to uncover more Rimbaldi findings, Sydney and Vaughn turn the tables on an old foe; the Taiwanese scientist and torturer "suit and glasses. Also, Katya expresses her attraction to Jack.
- After she managed to prove her innocence to FBI, Sydney is sent to Vienna to retrieve data from SD-6 spy in Russian Embassy. There she runs into Noah Hicks, her ex who broke her heart and left her without a word few years earlier. Meanwhile, Sloane promises Sydney to help her find her mother and Jack is losing his mind because of it.
- Sydney's life and cover as a double agent is placed in mortal danger when Sloane starts assuming that she is the mole. Dixon's life is at stake after the mission that went wrong. Meanwhile, Will realizes that his investigation of Kate Jones may be more dangerous than he thinks after he gets a call from the person "on the other side" of her pin.
- Jack's illness has caused him to hallucinate about a cure among other things. As a result, Sydney must recreate the time when Jack was working for the CIA and hid the only man who might be able to help him now. For this, Sydney must role play her own mother. Meanwhile, Sophia moves in with Sydney and Nadia.
- While Sloane awaits the outcome of his sentencing for treason, a mysterious associate of Gordon Dean approaches him for a favor in exchange for persuading the judges to rule in favor of acquittal. Meanwhile, Sydney and Tom must try to convince Rachel to help them catch the fugitive Gordon Dean who moves his operations to more secure locations. Sydney and Rachel return to the ruins of the Shed's offices in Prague for Rachel to reconstruction Dean's computer server so Tom and Dixon in the Cayman Islands can empty out Dean's bank accounts. Although they are successful, Dean discovers that Rachel is still alive which puts both her and Sydney in grave danger when they are trapped in a car that's hanging by an electromagnet controlled by Dean and his lethal associate Peyton who threaten to drop the hovering car unless Rachel's location is revealed.
- Vaughn and Sydney, searches for Vaughns father, and the word Nightingale. Getting help from her father, telling him that Vaughns father might still be alive. Jack Bristow and Sloane have their own agenda. Following Jack Intel, Sydney and Vaughn goes to Munich. Dressed as a German beer maid, Sydney roughly pursued an investment banker to give her information. They find out that Nightingale is still an active experiment, in an atomic plant in Siberia. They go on a mission to the plant. Which turns out to be very dangerous for both Sydney and her father.
- When Sydney gets bitten on the neck by a missing in action CIA agent, she soon finds out that she has been infected by a experiential hallucinogen, causing her to slowly lose touch with reality. Vaughn and Jack must race against the clock to find an antidote before Sydney puts her life (and others next to her) into danger.
- Sydney and Tom travel to Marseilles, France when they discover that Renée has stolen the cryo container which contains the cryogenically frozen body of her supposedly dead father. But they soon find themselves under siege in Renée's warehouse hideout by a group of mercenaries who want to reclaim Renée's father when he awakes up from his cryo-induced sleep... so it appears. Meanwhile, Rachel and Dixon travel to San Francisco to assist Marshall in the break-in of a vault facility to copy files to learn more about Renee's father. Elsewhere, Sloane takes matters into his own hands to get himself back into APO and continue his quest to find a cure for Nadia by influencing/blackmailing a influential senator to let him have full access to the CIA's accessories.
- Vaughn presents Sydney with a moral dilemma that includes Sloane's ill wife, Emily, in order to fulfill the mission whose outcome is an unpleasant surprise to everyone. SD-6 goes after Will when he comes too close. Meanwhile, Francie is dealing with her broken heart.
- On his own and desperate to find out more about his supposedly-dead father, Vaughn is pressured into a rogue operation for an unknown organization in exchange for information on the whereabouts of his father. He gains more than he bargained for in the deal. Meanwhile, Nadia is meeting with her aunt, Katya Derevko, in order to learn more about her mother, but Sydney doesn't trust Katya's motives.