Williams was a self-taught photographer with an active career beginning in the 1960s. He travelled in Europe through the late 1960s returning to Australia in 1969. In 1974, he and his partner Ingeborg Tyssen (d.2002), Paul Cox and Rod McNicol established the Photographers Gallery, Melbourne. By 1976, he was head of photography at the Sydney College of Arts, retiring to Tasmania in 1988.