I read Left Hand of Darkness, The Dispossed, and Earthsea a while ago, and have recently been going through her other books as and when I find them in charity/second hand book shops/fop. Big big fan. I hope her documentary does become available in the UK.
Left Hand and Dispossed are amazing. the Earthsea books are all good also, although I think I preferred the first two and Tales From Earthsea.
I really enjoyed her Birthday Of Worlds collection and Eye Of The Heron.
The Orsinian Tales, Lavina, Winds Twelve Quarters Vol1, Planet Of Excile, and Lathe Of Heave collection were good but not amazing.
Also read the Unreal & The Real Vol 1, and have Vol 2 to read next. And then I will need to find some more of her books to read!