Prog
Greg Lake - ELP, King Crimson
John Wettin - King Crimson, U.K.
Francesco Di Giacomo - Banco del Mutuo Socorrso (Italian prog band) / 5 octave range, beautifully expressive.
Dimetreo Stratus - Area (Italian prog band) / 5 octave voice, could sing up to 4 tones at once, expressive. His voice was studied by several universities around the world.
Gentle Giant - I mention the entire band, because of their complex multi part vocals. Saying they were inventive is an understatement.
Daniel Gildenlow - Pain of Salvation / 5 octave range, power to spare, dynamics, great intonation, and emotion.
A few more: Jon Anderson (Yes), Peter Hammill (Van Der Graaf Generator), Alberto Piras (Deus ex Machina), Peter Gabriel (with Genesis).