Here's a 1965 Syd Barrett song recorded as a demo tape with Pink Floyd before they started calling themselves Pink Floyd. It's called Lucy Leave, aka Lucy Lee in Blue Tights: download MP3
From the Pink Floyd hyperbase: Early Barrett song recorded on the first demotape late 1965. The band did not yet have the name Pink Floyd and guitarist Bob Klose was part of the band at the time. The song has not been officially released. The demo version is released with an italian book from 1996.
Thanks Spazz and RSM! RIP, Syd.