The film opens with Elise Clifton-Ward (Angelina Jolie) being followed by French Police, working with Scotland Yard under the direction of Inspector John Acheson (Paul Bettany). Acheson has spent years hunting Elise's old lover, Alexander Pearce, who owes £744 million in back taxes and is believed to have received 20 million dollars worth of plastic surgery to alter his appearance completely. At a cafe, Elise receives written instructions from Pearce: board a train to Venice, pick out a man who resembles Pearce, and make the police believe that this decoy is Pearce himself. Elise burns the note, then manages to evade the police and board the train.
On the train, Elise picks Frank Tupelo, an American community college teacher. She spends much time with him, seeming to start a romance. In the meanwhile, the police have managed to salvage the ashes of her burned note and assembled them to extract information regarding her rendezvous as well as her ruse. But an informer from the police station mistakenly communicates to Reginald Shaw, a gangster from whom Pearce as accountant stole $2.3 billion, that Pearce is travelling with Elise on the train to Venice. Shaw immediately proceeds to Venice.
Elise invites Frank to stay with her at the hotel room that has been arranged for her in Venice. Pearce leaves further instructions for Elise to attend a ball. Elise abandons Frank, who is then chased by Shaw's men. While trying to escape from them, Frank is detained by the Italian police ostensibly for his own safety, only to have a corrupt inspector turn him over to Shaw's men in exchange for the bounty that has been placed on Pearce's head. Elise rescues Frank just before he is handed over, leading Shaw's men on an extended boat chase and escaping. She leaves Frank at the airport with his passport and money, urging him to go home for his own safety.
Elise is revealed to be a Scotland Yard undercover agent who may have become Pearce's ally. Because of her fears for Frank, she agrees to participate in a sting operation. At the ball, as Elise wanders around trying to spot Pearce in the crowd, an envelope is placed on the table in front of her by a man who then quickly disappears into the crowd. Elise sees that the envelope is for her, and believes that the man must be Pearce himself. She tries to follow him through the crowd, calling out his name, but is stopped by Frank who has managed to enter inside under a pretext.
Frank claims to be in love with her, and invites her to dance with him. But he is hauled away by the police, while Elise opens the envelope and finds a note mentioning a rendezvous point. She then heads off in her boat to this new rendezvous point. Shaw and his men tail her in their boat; both parties are followed discreetly by the police boat in which Frank is held handcuffed to stop him from obstructing the investigation.
When Elise arrives at the destination, Shaw takes her prisoner, threatening to harm her unless she reveals the location of the stolen money. The police monitor the situation inside the rendezvous room through audio and video links. Despite Elise's peril, Acheson repeatedly turns down police requests to intervene with their snipers. While the police are occupied in monitoring the situation, Frank escapes from the police boat and confronts Shaw, claiming to be Pearce who has undergone plastic surgery and offering to open the safe if Elise is allowed to leave safely. Shaw is skeptical and makes a counter offer that Frank should open the safe if he does not want to see Elise being cut up. Chief Inspector Jones (Timothy Dalton) arrives at the police stake-out, overrides Acheson, and orders the police snipers to fire into the room, killing Shaw and his men. Jones lifts Elise's suspension and also terminates her employment.
Acheson receives a radio message that Pearce has been found not far from the rendezvous point, and rushes to the location where police have detained the suspect. But the man claims to be just a tourist who has merely been following instructions texted to his mobile phone, to be present at certain locations, for which he has been receiving payments. Meanwhile, Elise tells Frank that she loves him, but she also loves Pearce. Frank then suggests a "solution" to this dilemma; to Elise's surprise, he opens the safe by entering the correct code, thus revealing that he is really Alexander Pearce. He and Elise then take the money and depart, leaving a cheque in the safe for the full amount of the taxes he owes. The police find the cheque when they return and blow the safe open. Acheson now realizes that Frank has indeed been Pearce all along, and wants to pursue him; but Jones determines that, with the taxes now paid fully, Pearce's only crime is that he stole money from a now-dead gangster. Jones orders the case to be closed. Frank and Elise sail away to a new life together, with Elise taking in and getting used to the new and completely altered face of her old lover.
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