Since taxidriver expressed an interest, here are the Scorpion's appearances through the summer of 1986 in chronological order:

Amazing Spider-Man 19 (Dec '64) 1st Mac Gargan
Amazing Spider-Man 20 (Jan ’65) 1st Scorpion - origin
Amazing Spider-Man 29 (Oct ’65)
Captain America 122 (Feb ’70)
Daredevil 82 (Dec ’71) Mr. Kline’s android, not the real Scorpy
Captain America 150-52 (June-Aug ’72) teamed with Mr. Hyde
Amazing Spider-Man 145-46 (June-July ’75)
Ms. Marvel 1-2 (Jan-Feb ’77)
Spectacular Spider-Man 21 (Aug ’78)
Marvel Team-Up 106 (June ’81) adds blaster to tail mechanism
Avengers 222 (Aug ’82) with Egghead’s Masters of Evil
Amazing Spider-Man Annual 18 (1986)

Cei-U!
I summon the studly stinger!