When looking at a character's story arc over a number of movies, it's important to make the distinction between a character's story and a character's arc. Marvel characters such as Rhodey have had a very compelling story, going from Tony Stark's military friend to fully-fledged War Machine, but, consistently being an army vet, his character has not undergone as huge a personal transformation compared to someone such as Tony Stark or Thor.
Marvel has used the last 23 films to showcase its repertoire of amazing characters and through compelling and emotional storytelling, audiences have seen these characters grow massively. Only time will tell what's in store in the future for some of these heroes.
10 Bucky Barnes
Steve Roger's best friend since childhood, Bucky Barnes first appeared in Captain America: The First Avenger and still continues in the role to this day. Ever since Bucky fell off the train in 1945, many fans of the comics knew what was in store.
Bucky has suffered through Hydra's brainwashing, to dealing with the mistakes he made during his time as The Winter Solider. Fans saw how much his past life haunted him in Captain America: Civil War and chose to go back under the ice until he could trust his mind. Bucky then returns a hero in Avengers: Infinity War and Avengers: Endgame, fans will have to wait and see Bucky's arc develop even further in The Falcon and The Winter Soldier.
9 Loki
All Loki ever wanted was to be loved by his father as much as Thor was. Loki has been the villain of a couple of Marvel movies but 'died' a hero in Avengers: Infinity War. Starting off with Thor, Loki was obsessed with power and wanted the throne, and this arc continued throughout Thor: The Dark World.
In Loki's latter appearances leading up to and including Infinity War, showed him as a hero and in his own final words "Odinson", letting everyone know that despite all his differences with Thor, he was still his brother. Loki went from trying to kill Thor in the first movie, to being unable to stand the sight of Thor being tortured by Thanos.
8 Yondu
First appearing in Guardians of The Galaxy as an emotionless ravager, Yondu picked up Peter Quill on Earth as a young boy because he was able to fit into small places Yondu couldn't, good for theivin'. However by the end of Guardians of The Galaxy: Volume 2, fans saw Yondu evolve emotionally and personally into a father figure for Peter.
Comparing his first appearance to his last, it's definitely worth mentioning Yondu who took Peter on board to help with his crimes and then sacrificed himself to save his son to do something right for once in his life.
7 Hawkeye
At the end of Avengers: Assembled, some fans were left disappointed that for the majority of the film, Hawkeye was simply one of Loki's minions. In return, Marvel gave him huge character development in Avengers: Age of Ultron where it was revealed that he had a wife and kids.
Continuing through to Avengers: Endgame, Hawkeye went from S.H.I.E.L.D hitman to family man and mentor, to a fugitive in Captain America: Civil War, to be almost completely void of hope and a mindless assassin in Avengers 4.
6 Hulk
Bruce Banner has certainly been through his own transformation since his first appearance. Banner got so low at one point that he put a bullet in his mouth, only for the Hulk to spit it out. Banner/Hulk became Avengers in Avengers: Assembled, and then public enemy number 1 in Avengers: Age of Ultron.
Banner was also given a love story with Natasha Romanoff that didn't hugely pan out, and some fans weren't a fan of. But once Banner started looking at Hulk as the cure, he created the best of both worlds in a way that ended his ongoing feud with the Hulk and helped him live a fairly harmonious life.
5 Nebula
The story of Nebula and Gamora goes back to way before they were introduced in Guardians of The Galaxy. Since she was younger, Nebula was always bested and tortured by Gamora in combat, to her father's pleasing.
It was in Guardians of The Galaxy: Volume 2 that audiences fully saw the extent of Nebula's horrible life and the impact it had on her. Fans discovered that Nebula was not just an evil daughter of Thanos, but a lonely, broken person who just wanted a sister. The arc was highlighted in Avengers: Endgame when Nebula interacted with her past self in the third act.
4 Spider-Man
First appearing in Captain America: Civil War as a kid from Queens turned friendly Neighbourhood Spider-Man, Peter Parker was taken under Tony Stark's wing and mentored into becoming someone who doesn't need a suit to be a hero.
Peter has grown massively over his five-movie arc and went from battling super-soldiers in airports to alien armies in Endgame. Spider-Man: Far From Home saw Peter come into his own without the help of Tony Stark.
3 Captain America
One of the saddest but most satisfying endings in the MCU was certainly Captain America. Throughout his 7 appearances, Cap has always tried to do what is right and there have been times when that meant different things for Steve Rogers. In The First Avenger, Steve fought against Hydra which was clearly the right thing to do. In Captain America: The Winter Soldier, Steve began to see the world as more grey instead of black and white and Civil War showed Steve being more selfish as he fought to defend Bucky from Iron Man.
Although it's unlikely that Chris Evans will return, Cap managed to set aside his differences with Tony, save the universe, and get his love story ending with Peggy Carter, a character who was present in some form in every Captain America movie.
2 Iron Man
Back in 2008 when fans were introduced to Tony Stark, he was a genius, billionaire, playboy, philanthropist, and even by the end of the first movie, he had changed. After seeing what his weapons he could do, he shut them down and focused on righting his wrongs.
After settling down with Pepper, mentoring Peter Parker and sacrificing himself to save the world, it's hard to imagine the Tony Stark that we saw in Endgame being the same Tony Stark as was revealed in the first Iron Man movie.
1 Thor
Thor has arguably had the harshest life of any of the Avengers. He lost his worthiness and hammer in his first solo film before regaining both but losing his brother, meanwhile undergoing a huge personal transformation from a battle-hungry boy to a worthy heir to the throne. Thor: The Dark World saw him lose his mother and his brother again before losing his hammer (again) and his father in Thor: Ragnarok.
Once he learned that he did not need Mjolnir to be a hero he became the fully-fledged God of Thunder and was at the top of his game. But failing to kill Thanos and, by extension, failing to save his friends from turning to dust put Thor into a pit of despair and in an incredibly dark place, even after all he lost before. Thor then returns to his strongest by the third act of Endgame and was instrumental in defeating Thanos.
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