It's not long now till the highly anticipated arrival of Tom Holland as the Marvel Cinematic Universe's iteration of Spider-Man/Peter Parker. Next year's [Captain America: Civil War](tag:994409) will see Spider-Man swing into action alongside the Avengers, and with all the material available to work with on the Spider-Man/Avengers side of things it shouldn't be too difficult to find a place for him in the team.
Spider-Man has a long and complex history with the Avengers, sometimes as part of the team, sometimes swinging solo alongside them, sometimes as part of other superhero teams and sometimes absolutely saving their asses...
Avengers Vol 1, 1: The Mighty Avengers Meet Spider-Man!
Spider-Man first met up with the Avengers way back in 1964 in issue 11 of the Avengers comic book. Prior to this issue Iron Man (Tony Stark) had gone missing due to him having problems with the arc reactor, so the force of the team is weakened. At this point the time-travelling supervillain Kang the Conqueror (Nathaniel Richards) has been previously defeated by the Avengers, and so he returns to take revenge upon them whilst Iron Man is away. He decides the best way to do this is to create a robot version of Spider-Man to try and trick them.
The Spidey-Bot, posing as Spider-Man and claiming to know where Stark is, lures the Avengers to a temple where Kang lies in wait. He attacks them with nerve gas and the Robo-Spidey defeats them one by one. It all looks pretty bleak, until the real Spider-Man shows up and defeats the robot, saving their lives.
Spider-Man later asks if he can join the team, but is denied membership. Talk about ungrateful.
Marvel Two-In-One Annual Vol 1, 2: Death Watch
Spider-Man comes to rescue the Avengers again when they're captured by Thanos in 1977. He's not going it alone this time though, instead teaming up with the Thing from the Fantastic Four. Haunted by dreams of the Avengers battling Thanos in space, they head out to find out just what the hey is going on.
Aboard Thanos' ship they battle his forces and eventually the big bad himself. The fight spills into the stasis room where the Avengers (and Captain Marvel) are being held. Spider-Man manages to free them from stasis by doing the only logical thing - throwing himself at the machine holding them, and breaking it.
He then manages to (accidentally) free the Soul Gem within which the soul of Adam Warlock is contained. Warlock wastes no time in turning Thanos to stone, which is really going to put a crimp on his vacation plans.
Avengers and the Infinity Gauntlet 1-4
2010's Avengers and the Infinity Gauntlet non-canon miniseries is a comedic retelling of the original Infinity Gauntlet arc. It sees the universe in peril as Thanos (yep, him again) has now gained control of all six Infinity Gems. To impress Death, who he's a little bit in love with, he wipes out half the population of every planet.
After half the population of Earth, including the superhero population, is wiped out, a new Avengers team is assembled to find out what happened. Spider-Man, Hulk, Ms. Marvel, Wolverine and Doctor Doom (yep) are chosen to head into space to face Thanos.
Inevitably, Doctor Doom tries to betray the team and swipe the Gauntlet for himself (surprise surprise). However, he is unable to wield the Gauntlet (cause he's actually not the real Doctor Doom - actual surprise!) so it's Spidey's time to shine again. He manages to get a hold of it and uses the Gauntlet's powers to erase the entire adventure from history, restoring the timeline and reversing all the destruction and death wrought by the Mad Titan.
Good job Spider-Man. Even though you and Thanos are the only ones who know what you did. We know man, we know.