Green Goblin- Amazing Spider-Man #39
In The Amazing Spider-Man #39 the Green Goblin captures and unmasks Spider-Man. This is important because unmasking a super hero strips them of all safety found in having a secret identity and, from that point, Green Goblin is able to attack Peter Parker in ways that no other villain ever could. Throughout the rest of this list you will see attacks on Peter's emotional stability and family life that reach beyond the usual super hero/ super villain dynamic.