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Ethan Hunt (Tom Cruise) is an agent of an Impossible Missions Force (IMF) team, an unofficial branch of the CIA, led by Jim Phelps (Jon Voight). The team assembles for a mission in Prague to prevent an American diplomat from selling the Non-official cover (NOC) list - a comprehensive list of all covert agents in Eastern Europe. The mission goes hopelessly wrong, resulting in the deaths of the diplomat and every team member except Hunt. Fleeing the scene, Hunt meets with Eugene Kittridge (Henry Czerny), the CIA-based director of the IMF, at a café. Kittridge discloses that the NOC list in Prague was a fake meant to draw out a mole who has infiltrated the IMF and made a deal to sell the list to an arms dealer known as "Max." Suspicion now falls on Hunt, the only survivor of the botched mission, who makes a daring escape from the café and flees into the city.

Hunt returns to the IMF safe house, where he discovers that fellow agent Claire Phelps (Emmanuelle Béart), Jim Phelps's wife, actually survived the mission. He begins correspondence with Max (Vanessa Redgrave), warning her about the fake NOC list and offering to deliver the real one in exchange for $10 million and a face-to-face meeting with the mole, nicknamed "Job." Max agrees to the deal and gives Hunt a cash advance, which he uses to hire two blacklisted or disavowed intelligence agents: computer expert Luther Stickell (Ving Rhames) and pilot Franz Krieger (Jean Reno). Hunt, Stickell, Krieger, and Claire infiltrate the heavily fortified headquarters of the CIA in Langley, Virginia, and successfully steal a copy of the full NOC list before escaping to a safe house in London. Once there, Hunt discovers that his uncle and mother have been falsely arrested for drug trafficking in an attempt by Kittridge to lure him out of hiding. This infuriates Hunt, and he contacts Kittridge, who offers to drop the false charges the moment Hunt surrenders to authorities. Hunt stays on the line long enogh for Kittridge to trace him to the London area, then hangs up and finds Jim Phelps standing right next to him.

Phelps, presumed dead in the Prague operation, says that Kittridge is the mole and is trying to tie up loose ends by arresting Hunt. Hunt reflects on this, while mentally piecing together clues he has discovered along the way and concluding that Phelps is the mole, Job. Hunt pretends to accept the story, understanding that Krieger has assisted Phelps, but is still doubtful about Claire's place in the conspiracy. The next day, Max and Hunt arrange to meet aboard the TGV en route to Paris, with Claire and Stickell aboard to provide backup. Kittridge is also aboard, having recently arrived in London and received tickets for the TGV and a video watch from Hunt. Aboard the train, Hunt delivers the NOC list to Max, who directs him to the luggage compartment to find Job and his money. Max then attempts to transmit the NOC list to a server, but Stickell activates a jamming device to prevent the upload. Claire, observing Kittridge's presence aboard the train, vacates her seat and meets with Phelps in the luggage car, confirming her part in the conspiracy. A silent "Phelps" slowly peels his face away, showing it as a mask and revealing himself as Hunt. They are interrupted by the arrival of the real Phelps, armed and demanding that Hunt hand over the money paid to him by Max. Hunt does so, then puts on a pair of glasses with a camera built into the bridge; the image of Phelps' face is transmitted to the video watch carried by Kittridge, giving the latter undeniable proof of Job's true identity.

Claire tries to persuade Phelps not to kill Hunt, but he kills her instead, knocks Hunt down, and climbs up to the roof. Krieger has been following the train in a helicopter and is waiting to extract Phelps. Hunt recovers and follows Phelps, impeding his efforts to escape and tethering Krieger's helicopter to the train as it heads into the Channel Tunnel. The fight continues, with the helicopter now following the train inside the tunnel. The two fight atop the wind-swept train before Phelps disconnects the helicopter from the train and attempts to escape. Hunt follows, leaping onto the helicopter's landing skids and attaching explosive chewing gum to the windshield. The ensuing explosion kills Phelps and Krieger, with Ethan narrowly escaping. Now in possession of the NOC list and Max's true identity, Kittridge reinstates Stickell as an IMF agent and drops his investigation against Hunt, who resigns from the IMF. As he flies home, a flight attendant approaches him and asks, through a coded phrase, if he is ready to take on a new mission.

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