Marvel's Avengers has just added another playable character, the long-promised PlayStation-exclusive Spider-Man. Though the wall-crawler is free and you don't have to earn him through gameplay, you have to find him and trigger a cutscene before you can start spinning webs, any size.
Before you start, make sure you've updated to the latest version of Marvel's Avengers on PS4 or PS5. He's a PlayStation-exclusive character, so if you're playing on PC or Xbox, then sorry, no Spidey for you. If you have the latest version installed, you'll see Spider-Man on the main menu, hanging upside-down on the left side of the hero line-up. However, if you go into the hero selection menu, you'll find a prompt saying you need to find Spider-Man on the helicarrier before you can start playing as him.
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Once at the Chimera, though, Spider-Man himself is no where to be found. He's not in any of the crew quarters or in the hangar bay or on-deck. In fact, he isn't in the helicarrier at all, but rather, outside of it. To find him, look at the left side of the front windows on the main deck. One of the windows is covered with a "Suspicious Web," and investigating that will trigger a cutscene explaining how Spidey falls in with the Avengers.
Though Spider-Man casually references some story context for why he came looking for the Avengers in the first place, he notably has no story missions of his own. Instead, his story is delivered primarily through audiologs and motion comics that are unlocked through finishing his quest line of challenges, called With Great Power.
That also means that leveling him up to unlock his abilities will be a bit different than the other post-launch characters, the two Hawkeyes and Black Panther. Rather than playing through new story content to get started unlocking his abilities, you'll have to revisit older missions or multiplayer to level him up. Developer Crystal Dynamics has said this is because it wanted to focus most of its efforts on content that all platforms can play, like the upcoming Klaw raid.