Behind "Knucksie" and Wilhelm, I might go with Eddie “Knuckles” Cicotte, who is considered the first to master the pitch.
Cicotte had some of the best years of any pitcher of his era in 1913, 1917, and 1919 when he was a combined 75 wins vs. 30 losses during those years and an ERA well below 2.00 each of those seasons.
Cocotte went 21-10 in 1920 before he was banned from baseball as part of his being a major part of the Black Sox scandal. Had he continued playing a few more years (and avoided scandal), he may very well have become HOF worthy.
Wilbur Wood was a knuckleballer that also put up some big numbers in the early 1970s.
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