He was a baritone vocalist. He began his career with lifelong friend Eddie Kendricks in a group called The Primes (inspiration for The Primettes, who would later become The Supremes.)
He and Kendricks became part of The Temptations in 1961.
He sang lead on the Temptations song "Don't Look Back".
Williams, who had struggled with alchol and poor health, was found dead in his car of a gunshot wound.