Otto takes it for the pimp slap alone.
Amazing Spider-Man #1: The Chameleon
Amazing Spider-Man #2: The Vulture
Amazing Spider-Man #3: Doctor Octopus
Amazing Spider-Man #4: The Sandman
Amazing Spider-Man #6: The Lizard
Amazing Spider-Man #9: Electro
Amazing Spider-Man #10: The Big Man and the Enforcers
Amazing Spider-Man #13: Mysterio
Amazing Spider-Man #14: Kraven the Hunter
Amazing Spider-Man #15: Sandman
Amazing Spider-Man #20: The Scorpion
Amazing Spider-Man #25: Spencer Smythe/ Spider Slayers
Amazing Spider-Man #28: The Molten Man
Amazing Spider-Man #36: The Looter
Other (Please Specify)
Doc Ock's debut. The first one to beat Spidey in a humiliating way and the first time that Spider-Man was thinking of quiting. It was obvious that Dr Octopus was destined to be a major force in Spider-Man mythos.
" I am Loki Scar-Lip, Loki Skywalker, Loki Giant's Child, Loki Lie-Smith. I am Loki, who is fire and wit and hate. I am Loki. And I will be under an obligation to no one."
Previously known as Nefarius
Doctor Octopus' origin is, in my opinion, one of the single greatest comics ever so I'll probably just go for that.
There are some good secondary choices, I really like the Vulture and Mysterio's debuts.
It always tickles me that Max Dillon is shown to be a jerk before the accident, then is just a super-powered jerk after. He never really changed since. I also have a soft spot for the Looter, as he's just kind of crap. I love a lame super-villain.
"Has Sariel summoned you here, Azrael? Have you come to witness the miracle of your brethren arriving on Earth?"
"I WILL MIX THE ASHES OF YOUR BONES WITH SALT AND USE THEM TO ENSURE THE EARTH THE TEMPLARS TILLED NEVER BEARS FRUIT AGAIN!"
"*sigh* I hoped it was for the miracle."
Dan Watters' Azrael was incredible, a constant delight and perhaps too good for this world (but not the Forth). For the love of St. Dumas, DC, give us more!!!
Mysterio origin is my favorite and is one of the first villains I really appreciate along the Green Gobling and of course Doc Ock.