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He was the secret head of HYDRA and its top undercover operative inside the United States Government, S.H.I.E.L.D., and the World Security Council who used HYDRA's forces within S.H.I.E.L.D. to give HYDRA absolute control over the world. His plan, Project Insight, was foiled by Captain America and the loyal remnants of S.H.I.E.L.D., and was ultimately killed by former longtime friend, Nick Fury.
Alexander Pierce is a HYDRA agent who infiltrated the World Security Council, who oversaw S.H.I.E.L.D. During a hostage situation in Bogota, he met S.H.I.E.L.D. agent Nick Fury, who successfully saved the hostages, including Pierce's daughter. Pierce was surprised by Fury's performance and later made him the director of S.H.I.E.L.D.
Setting Up His Plan
Decades later, the influence of HYDRA over S.H.I.E.L.D. has grown stronger, and a set of three heavily armed Helicarriers are built under "Project Insight." The Helicarriers were allegedly supposed to form a security network to protect the Earth, but HYDRA actually desired to use them to target and kill approximately 20 million people selected by Arnim Zola's algorithm, any individual which would pose a threat for Hydra's new world order.
After discovering the hijacking of a S.H.I.E.L.D. boat by Georges Batroc was actually planned by Fury in order to recover confidential files related to the Project Insight, Pierce deploys the Winter Soldier to kill him.
After being attacked by the Winter Soldier, a heavily injured Fury contacts Captain America and tells the Captain not to trust anyone as S.H.I.E.L.D. had been compromised, before seemingly being assassinated.
Following Fury's apparent demise, Pierce talks with Captain America, and discovers that Rogers has hidden something from him, likely meaning that his plans were compromised due to something Nick Fury may have said to him.
Pierce deploys other corrupt S.H.I.E.L.D. agents to capture Cap, who goes undercover along with Black Widow. A new assignment is given to the Winter Soldier by Pierce, to kill Captain America and Black Widow. After gaining information related to the true objective of Project Insight from the hand of Jasper Sitwell, Rogers, Romanoff and their ally Sam Wilson/Falcon are captured by S.H.I.E.L.D., but they soon escaped captivity.
Pierce proceeds to continue with his plan, but as S.H.I.E.L.D. is getting prepared to deploy the Helicarriers, Captain America infiltrates the Triskelion and reveals by loudspeaker the truth of HYDRA influencing S.H.I.E.L.D. and prompts every clean agent to stand up against HYDRA.
While Captain America and Falcon infiltrated the Helicarriers to modify their programming to change the targets from the people selected by Zola's algorithm to the Helicarriers themselves, Black Widow rescues the rest of the members of the World Security Council, who have been taken hostage by Pierce, and forces him to help her and Nick Fury, who reveals his survival to Pierce, to unlock every single one of S.H.I.E.L.D./HYDRA's secrets and upload them to the Internet. However, Pierce attempts to use a remotely-controlled miniature explosive he had hidden in Black Widow's clothes to force Fury to let him go.
Using a micro-EMP, Black Widow disables the bomb, Fury subsequently shoots Pierce twice through the heart.
As he lies dying, witnessing his fleet and plans in destruction, Pierce utters "Hail Hydra..." and dies. His partners-in-crime would then later meet their fates at the hands of S.H.I.E.L.D in the battle. Except from Bucky, who is beginning to remember both his past and who he really is: Bucky.
In a battle on one of the helicarriers, the Winter Soldier shoots Rogers. However, it turned out that death is not taking him yet, as Rogers immediately replaces the final chip, allowing Hill to take control and destroy all three vessels. The Helicarrier carrying Rogers and the Winter Soldier crashes into the side of the Triskelion, critically wounding Agent Rumlow, who had earlier tried to capture Rogers, while Wilson escapes.
The Helicarriers are destroyed in process, and HYDRA's secrets are released to the world. Rogers falls into the river, but is suddenly saved by Winter Soldier who then leaves, now returned to his former self and goes to find out more about his past. Alexander Pierce himself on the other hand, was shot dead by Nick Fury then dies after saying "Hail Hydra" as he watches the ship plunges into the water.
Five years after the death of half the living beings in the universe, the remaining Avengers and Guardians concoct a plan to go back to the past and collect the Infinity Stones from different points in time and use them to reverse Thanos' actions; Captain America, Iron Man, Ant-Man and Hulk going back in time to the Battle of New York to retrieve the Space Stone, Mind Stone, and Time Stone. As the Avengers are trying to leave Avengers tower with the apprehended Loki, Pierce arrives and stops them, demanding that Loki and the Tesseract/Space Stone should be handled by the American government, though the 2012 Iron Man claims that they are being taken care of by a higher authority, as Thor intends Odin to take care of Loki.
While Pierce argues with Stark and Thor, in order for them to get their hands on the Tesseract, Iron Man has Ant-Man disable his past self's Arc Reactor for a diversion, resulting in him having an attack which distracts Pierce and the others long enough for him to get the case holding the Tesseract. However, the plan fails when Iron Man loses the case because of the past Hulk, causing Loki to get his hands on it instead and use its power to escape, much to Pierce and the others' confusion. In the short-lived Nexus event created afterwards by Loki's escape, it's likely that due to indirectly causing an scene and distracting everyone, Pierce was held responsible for allowing Loki to escape and was possibly punished for that.
However, as the Time Variance Authority led by Judge Ravonna Renslayer had Loki taken into custody and reset the timeline to how it was back before Loki escaped, it's presumed that everything went back to normal like it happened in the original timeline, so Pierce was likely unable to claim the Tesseract and kept working for HYDRA until his death at Nick Fury's hands.
In the comics, Alexander Pierce is a much younger field agent. Robert Redford let slip that he accepted the role because he wanted to portray a villain; leading some to speculate that Pierce is a cover for Aleksander Lukin, who is the man who controlled the Winter Soldier in the comic books.
In an interview with USA Today, Samuel L. Jackson revealed that Alexander Pierce is a member of the World Security Council, but was not present during the events of The Avengers.
Even though he is the main antagonist, he did not fight Captain America nor engage him in the film's climax with only his enforcer Winter Soldier being Captain America's final enemy in the film.
Pierce may also be a substitute for Red Skull, whose actor from the first film did not wish to reprise his role. In the comics, Red Skull once somehow became US Secretary Of Defense under the alias Dell Rusk during the Avengers: Red Zone storyline, and was not exposed until a scheme of his was enacted. Pierce being a real person who eventually turned traitor also makes more sense than a known, active, wanted supervillain making his way into a highly scrutinized position.
Worth noting that, prior to the movie's release, there was much speculation that he was the Red Skull in disguise (just as Dell Rusk is).
Robert Redford retired from acting shortly after his appearance in Avengers: Endgame, making this his final film role in his career. However, he did come out of retirement briefly to play as a fictionalized version of himself in the HBO drama series Watchmen.