5. Helmut Zemo – Captain America: Civil War (2016)
Superhero movies, particularly those of the MCU, are pretty predictable. The heroes are the good guys, the villains are all pure evil, and there’s no real gray areas. Captain America: Civil War flipped that on its head though, with the Avengers taking sides against one another after becoming embroiled in a political firestorm.
Though it’s not revealed until later in the film, these events were all masterminded by Helmut Zemo. His plan involved using the Winter Soldier’s brainwashing to assassinate the King of Wakanda, sparking an all-out war between superheroes in order to tarnish their public image. It pretty much works exactly as he planned, which isn’t revealed until after it’s already happened.
Though Zemo is undoubtedly the villain, his motivations are relatively pure. The Avengers’ fight with Ultron destroyed his home and killed his wife and child, making his vendetta somewhat understandable. In the end, the only way that the Avengers thwart Zemo is by arresting him, by which time he’s already taken revenge on the heroes.