Mick Foley is credited with innovating the Cactus Clothesline (running clothesline carrying both wrestlers over the top rope and onto the floor)
Steve Bordon is credited with the Stinger Splash (flying full body splash against the corner post)
It is unknown who invented the Scorpion Death Lock/Sharpshooter, but Bret Hart claims Sting taught him the move.
Brunno Sammartino is credited (to the best of my knowledge) with innovating the Pendulum Backbreaker.
Taka Michinoku invented the Michinoku Driver.
Gory Guererro generally innovated the moves named after him.
I think the Doomsday range of moves (one member of a team elevates the opponent on his shoulders while the other attacks from the top rope) were innovated by the Road Warriors during their time in Japan. Not sure, maybe someone can clarify.