This is inspired by a Time Magazine Article. Feel free to criticize, or post your own.
60's- Amazing Spider-Man #31-33
Writer- Stan Lee
Artist- Steve Ditko
This story's most famous for the opening sequence of the third chapter, but I also loved Peter's horrific first day in college, the depth of his love for Aunt May, Spider-Man getting really pissed off, the return of Curt Connors, how Peter upset Betty, Peter's relationship with the Bugle, and a doctor asking why teenagers can't idolize Peter, instead of someone like Spider-Man, which I just realized is the perfect response to critics who wonder why people like comic book characters so much.
70's- Amazing Spider-Man #121-122
Writer- Gerry Conway
Artist- Gil Kane
It's almost unfair that Conway got to write a comic book story this good. It includes probably the two most memorable deaths in the MArvel Universe, "snap", excellent battles between the hero and villain, and perfectly alters the relationships between Peter, and MJ, and Peter, and Harry. My favorite Spider-Man story ever.
80's- Amazing Spider-Man #248 "The Kid Who Collects Spider-Man"
Writer- Roger Stern
Artist- Ron Frenz
The 80's were a very good decade for Spider-Man with Peter David's run on Spectacular, Kraven's Last Hunt, Spider-Man VS. Wolverine, the introduction of Venom before he became overused, and Roger Stern's stories pitting Spider-Man against villains he'd never fought before. But my favorite story from this time period has Spidey talking with a young fan. Great moments include the fan comforting Spider-Man after hearing about Uncle Ben, the "retractions" album, and the last 2 panels.
90's- Amazing Fantasy #16-18
Writer= Kurt Busiek
This is the decade when I came into Spider-Man, and the decade I care the least for. This mini series was set between the never explored period between Amazing Fantasy #15, and Amazing Spider-Man #1, introduced compelling new villains, and perfectly portrayed a grief-stricken Peter pondering what to do with his future, as the other superheroes were emerging.
2000's- Spider-Man 2
Director- Sam Raimi
Writers- Alfred Gough, Miles Millar, Michael Chabon, Alvin Sargent
Actors- Tobey Maquire, Kirsten Dunst, James Franco, Alfred Molina, Rosemary Harris, JK Simmons
An unorthodox choice, and not meant to imply that the current comic books are bad. I loved the special effects, resolution of Peter and Mary Jane's romance, cameos of the dead from the first movie, the continuing story of Harry Osborn, the best movie battles ever, Rosemary Harris's performance as Aunt May, and more.