The Fan man.. The way he maneuvered that schute into a square ring from high above is pure skill at its best. Of course he took a lot of shots while being carried out of the ring, so I can't give him points for defense.
I'll throw Kid McCoy's name into the mix. He invented the corkscrew punch. McCoy was noted for his "corkscrew punch"–a blow delivered with a twisting of the wrist. According to McCoy, he learned the punch one evening while resting in someone's barn after a day of riding the rails. He noticed a cat strike at a ball of string and imitated its actions. Whether true or not, McCoy was known as a fast, "scientific" fighter who would cut his opponents with sharp blows.
William Sherriff invented the Burgermeister Half Hock Throw which revolutionized the game in the 1880's.