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Pistol-based heroes/villians:
Grifter (Pistol/Super Reflex) Image Comics :Wildcats #1
Ghost (Pistol/Dark Armor? w/ phase shift) Dark Horse Comics: Ghost #1
Nick Fury (Pistol/Devices) Marvel: Not sure of debute
Scourge (Pistol/Devices) Marvel: Debuted Iron Man #195
Jonah Hex (Pistol/Invuln.) DC (as seen on JLU)
Ghost Rider (Pistol/Dark Armor) Marvel (the Western one, not the guy on the motorcycle. Seen in the West Coast Avengers.)
Johnny Thunder (Pistol/Super Reflex) DC (The western one)
Vigelante (Pistol/Super Reflex) DC (as seen on JLU)
Adam Strange (Pistol/Super Reflex w/ Flight) DC
Crimson Avenger/Scarlet Avenger (Pistol/Devices) DC: The Crimson Avenger debuted in Detective Comics #20. For reference, Batman debuted in Detective Comics #27.
The Sandman [Original] (Pistols/Devices) DC: Debuted in Action Comics #40
I hope that helps.
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Not to mention Hellsing's Alucard.