It's strange: I always liked most of their singles (both the depressing Sixties-era stuff as well as their Kings of Disco stuff a few years later), but I never owned any of their albums, or any of their singles.
Still, there were few more distinctive vocalists of that era than Robin Gibbs. Unless you count Ringo Starr (which sounds like a cheap shot, but I'm dead serious).
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By the way, the most effective use of a Bee Gees song on a soundtrack was not, as many naturally suppose, “Stayin' Alive” (or the rest of the “Saturday Night Fever” soundtrack album). It was “I Started a Joke,” on the dark (of course) 1989 meta-comedy Penn & Teller Get Killed, directed by Arthur Penn.