It may seem strange to see an Avenger listed as one of Spider-Man's enemies, but that's exactly what Iron Man became during Civil War. Friends at first, Tony Stark actually manipulated Peter Parker into revealing his secret identity, and didn't hesitate to try and take Spidey down by any means necessary when he defected to Captain America's team. They've worked together since, but Peter remains wary of Stark, and you can't blame him after Iron Man sent the Thunderbolts after him (Spider-Man might have died if not for the intervention of The Punisher). There's a lot of tension between the former friends!