OK gentlemen, my 2cents :
Acording to the book, "Crazy Fingers" By Annette Carson (... a bio on Jeff Beck, BackBeat Books, 2001) he, JEFF BECK, was the first ever muso to use a Fuzz-box live.
Jimmi Page and Jimi Hendrix saw this thing for the first time at various Jeff Beck gigs !
Now who was the first ever muso to use one in a recording - i have no idea !
So, because of this book, my vote goes to Jeff Beck as the first EVER to use one live !