Astronomy Domine - Pink Floyd
Easily the best of the Syd Barret era. You can hear touches of what you would hear later on, and the portions of the song sound very similar to the later recorded "Shine on You Crazy Diamond", but I think that was intentional. Of course a song about Syd would borrow harmonic structures from a song Syd was integral part of.
I understand fully why it was the only Syd Barret song to stay in the Pink Floyd repertoire to the end, and David Gilmour still performs it at solo performances.