Two years after the Battle of New York, Steve Rogers lives in Washington, D.C. and works for the espionage agency S.H.I.E.L.D. while adjusting to contemporary society. Rogers, along with his S.T.R.I.K.E. team and agent Natasha Romanoff, is sent to liberate hostages aboard a S.H.I.E.L.D. vessel from Algerian pirates led by Georges Batroc. Mid-mission, Rogers discovers that Romanoff has another agenda: to extract data from the ship's computers for S.H.I.E.L.D. director Nick Fury. Rogers returns to the Triskelion, the S.H.I.E.L.D. headquarters, to confront Fury and is debriefed about Project Insight: three Helicarriers linked to spy satellites and designed to preemptively eliminate threats.
Fury, unable to access the encrypted data that Romanoff recovered, becomes suspicious about Project Insight. On his way to rendezvous with Maria Hill, Fury is ambushed by assailants disguised as police officers, led by a mysterious assassin called the Winter Soldier. Fury escapes, sneaks into Rogers' apartment, and warns Rogers that S.H.I.E.L.D. has been compromised. Fury hands Rogers the USB flash drive that contains the data from the ship before being gunned down by the Winter Soldier, who escapes. Fury dies in surgery, and Hill recovers the body.
The next day, Rogers is summoned to the Triskelion by senior S.H.I.E.L.D. official Alexander Pierce. When Rogers withholds Fury's information, Pierce brands him a fugitive. Hunted by the agency, Rogers meets with Romanoff. Using data in the flash drive they discover an old S.H.I.E.L.D. underground base in New Jersey. There, they activate a supercomputer containing the preserved consciousness of Arnim Zola, who reveals that since S.H.I.E.L.D. was founded after World War II, HYDRA has secretly operated within its ranks, sowing global chaos in the hope humanity would willingly surrender its freedom in exchange for security. Rogers and Romanoff narrowly escape death when a S.H.I.E.L.D. missile destroys the bunker.
Rogers and Romanoff enlist the help of Sam Wilson, a former military parajumper whom Rogers befriended, and acquire his powered "Falcon" wingpack. After deducing that senior S.H.I.E.L.D. agent Jasper Sitwell is a HYDRA mole, they interrogate him until he divulges that Zola developed a data-mining algorithm that can identify individuals who might become future threats to HYDRA's plans. The Insight Helicarriers will eliminate these individuals around the world with their satellite-guided guns.
En route to S.H.I.E.L.D. headquarters, Rogers, Romanoff and Wilson are ambushed by the Winter Soldier and Sitwell is thrown into oncoming traffic. During the fight, Rogers recognizes the Winter Soldier as Bucky Barnes, his old World War II comrade, before being captured by S.H.I.E.L.D. They are rescued by a disguised Hill, who leads them to a hideout and Fury, who had faked his death. Fury plans to sabotage the Helicarriers by replacing their controller chips.
After members of the World Security Council arrive for the Helicarriers' launch, Rogers reveals HYDRA's plot to everyone at the Triskelion. Romanoff, disguised as one of the Council members, disarms Pierce. Fury arrives and forces Pierce to unlock access to S.H.I.E.L.D's database so Romanoff can expose HYDRA by leaking classified information. After a struggle, Fury shoots Pierce dead.
Meanwhile, Rogers and Wilson storm two Helicarriers and replace the controllers, but the Winter Soldier destroys Wilson's suit and fights Rogers on the third. Rogers fends him off and replaces the final chip, allowing Hill to take control and have the vessels shoot each other down. Rogers falls from the Helicarrier as it crashes into the Triskelion, where Wilson fights double agent Rumlow, who belonged to Rogers' S.T.R.I.K.E. team. Rogers lands in the Potomac River and is rescued by the Winter Soldier, who then disappears.
With S.H.I.E.L.D. in disarray, Fury destroys the last traces of his identity before heading to Eastern Europe in pursuit of HYDRA's remaining cells, under the cover of his apparent death. Romanoff appears before a Senate subcommittee and later gives Rogers a dossier on the Winter Soldier program. Both Rogers and Wilson decide to track down the Winter Soldier.
In a mid-credits scene, Baron von Strucker, at a HYDRA lab, proclaims that HYDRA has not finished its fight with S.H.I.E.L.D. before looking at two prisoners: one with superhuman speed, the other with telekinetic powers. In a post-credits scene, the Winter Soldier visits the Captain America exhibit at the Smithsonian Institution.
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