With Captain America: Civil War, as the friendly neighborhood Spider-Man got a first taste of the big-scale action and continued to gain more Avengers experience after facing Thanos in Infinity War.
During his six appearances thus far in the MCU, Peter Parker has transformed from a meek high school student to a powerful and independent hero. And though Peter matured as he owned up to his mistakes, he would have never reached this level of self-actualization without the help of several key people in his life.
Vulture
Adrian Toomes, portrayed by Michael Keaton, is the primary antagonist of Spider-Man: Homecoming, the first film in the eponymous superhero's MCU trilogy. Moonlighting as the Vulture, Toomes steals and repurposes alien tech, selling it to street-level criminals in order to provide for his family.
As the first major villain that the MCU's Spider-Man ever fought, Toomes showed Peter Parker that life as a superhero is not all fun and games. He pushed the friendly neighborhood wall-crawler to his limits, nearly killing him in the process, but ultimately proving Spider-Man to be every bit the hero he claimed to be.
Liz Allan
Liz Allan is Peter's former classmate, whom he has a massive crush in Spider-Man: Homecoming. Portrayed by Laura Harrier, Liz nearly initiates a relationship with Peter until her father is suddenly arrested for his supervillain activity, and her family moves out of state.
After the events of Homecoming, Liz would always represent something very important for Peter, a symbol of how the people close to him can be hurt by Spider-Man. Peter essentially ruined Liz's life by apprehending her father, yet it was the right thing to do nonetheless. Liz would only be the first of many whose life was turned upside-down by Peter's superhero alter-ego.
Ned Leeds
Ned Leeds, played by Jacob Batalon, is Peter Parker's best friend from high school and his designated "guy in the chair." Based on one of the several alter-egos for the villainous Hobgoblin in the comics, Ned seems to be one MCU character who may never become his comic book counterpart, much to the delight of his many fans.
Ned was the first person in Peter's life to discover his secret identity, henceforth becoming his closest confidant when it came to his vigilante activity. No matter how bizarre his life became after learning the truth, Ned always stood by his best friend, teaching Peter a valuable lesson about loyalty and friendship.
Mysterio
Jake Gyllenhaal's Quentin Beck, a.k.a. Mysterio, is not only the primary antagonist of one of the MCU's best villains ever. Pretending to be a superhero from another dimension, Beck is actually a con man with a mastery over special effects and a penchant for Peter Parker's new high-tech gadget.
Beck's betrayal in Far From Home taught Peter a difficult but powerful lesson in putting faith in his own instincts and being wary of those who would ask for his trust. The supervillain's contingency plan revealing Peter Parker to be Spider-Man also served to alter the very course of the young superhero's life, even if only temporarily.
Peter 3
Andrew Garfield's Spider-Man makes his exciting and long-rumored return in Spider-Man: No Way Home, in which he arrives from an alternate dimension following Doctor Strange's botched spell. Teaming up with Tom Holland and Tobey Maguire's Spider-Men, this variant of Peter Parker, affectionately titled Peter 3, helps defeat a team of multiversal supervillains at the Statue of Liberty.
Peter 3 quickly becomes a brother-like figure for Holland's Spider-Man, bringing with him his many years of experience as a superhero. He was able to teach his variant to learn from his failures--even the most painful ones--as he had done when he lost Gwen. Ultimately, he and Peter 2 helped usher Peter 1 through one of the most difficult and grief-laden nights of his life.
Norman Osborn
Willem Dafoe's Norman Osborn returns in No Way Home almost twenty years after his debut as the character in 2002's Spider-Man. Along for the ride is Norman's villainous alter-ego, the Green Goblin, who instigates a conflict between Spider-Man and the multiversal villains whom he is trying to rehabilitate.
Despite only spending one day with Peter, Norman would change his life profoundly, murdering his Aunt May with his glider. The seething rage that engulfed Peter thereafter nearly drove him to kill the supervillain, only to relent in the final moments and once more earn the title of Spider-Man.
Peter 2
Tobey Maguire, best known for portraying one of the best Peter Parkers, returns in No Way Home to help the MCU's Peter Parker defeat and cure several multiversal villains. Teaming up with Andrew Garfield's Spider-Man, the three superhero variants save the day on Liberty Island.
Peter 2 proved to be the most seasoned superhero of the Spider-man trio, whose experience played a massive role in helping Peter 1 grieve Aunt May's recent death. Maguire's character stepped in the way to keep Peter from killing the Green Goblin in retribution, preserving the young man's heroism in the process.
MJ Watson
Zendaya's MJ Jones-Watson is Peter Parker's girlfriend and closest confidant who, after becoming aware of his alter-ego, helps him defeat several supervillains that stand in his way. Once Peter's identity is exposed to the world, she sticks by her boyfriend and helps him weather the storm of the public's wrath.
MJ has proven to be the greatest love of Peter's life thus far, keeping him strong during the most difficult experiences of his life. Through her, Peter also learned the importance of selflessness, even choosing not to be with her in order to keep her safe.
Tony Stark
Robert Downey Jr.'s Tony Stark is the MCU's premiere superhero, whose tragic death is still a sore point for Marvel fans. He first recruits Peter during the events of Captain America: Civil War, later serving as the fledgling superhero's mentor during the early years of his career in the Avengers.
Tony's contributions to Peter's life must not be understated. It was he who pushed Peter into a new phase of superheroism, equipping him with a brand new suit and Avengers status. It was also Tony whose death destroyed Peter, sending him down a road of emotional turmoil that resulted in the events of Far From Home. Spider-Man was forced to grow into his own superhero brand to clean up a mess that his grief and self-doubt had caused.
Aunt May
Marisa Tomei portrays the MCU's version of Aunt May, who is the sole parental figure in Peter Parker's life. Discovering her nephew's secret at the end of Homecoming, May goes on to facilitate his career as Spider-Man until her death at the hands of the Green Goblin during the events of No Way Home.
May's and love for Peter when he had no one else helped turn him into the man that he has now become. For all intents and purposes, May was Peter's mother, raising him as her own. Her death shattered Peter, pushing him down a dark road, until he eventually comes to the conclusion that he can best honor his late aunt by showing others the same love that she had shown him all those years.