My vote goes for Kraven's Last Hunt.

Taken from wikipedia:

"Kraven hunts down Spider-Man, defeats him, and seemingly shoots him dead. Kraven then buries him, and donning a copy of Spider-Man's costume, seeks to prove himself superior at his adversary's former activities.

He roams New York, brutally attacking criminals. The culmination of these activities is Kraven's successful unarmed capture of Vermin, whom Spider-Man needed the help of Captain America to defeat. After two weeks, Spider-Man revives from the effects of the tranquilizer dart Kraven shot him with, and digs his way out of the grave. When Spider-Man confronts Kraven, the hunter does not fight back, considering himself the victor and his final point made.

Kraven then releases Vermin, who attacks Spider-Man, thinking him to the be the one who so brutally beat him before. Vermin is able to defeat Spider-Man, but Kraven intervenes before Vermin can kill him. He allows Vermin to go free, and tells Spider-Man he can pursue him if he desires, but that Kraven's hunting days have ended. While Spider-Man goes after Vermin, Kraven retires to his home, reminiscing about his past and the peace he now feels, and commits suicide with a rifle. He leaves a confession of his burying and impersonating Spider-Man for the police to find, complete with photographic proof. Spider-Man catches up with Vermin and lures him above ground, where sensory overload renders him helpless. He turns Vermin over to the police and goes home to his wife."

Makes me want to see a movie out of this arc .__.