My personal favourite LeGuin is Always Coming Home, which is kind of a multimedia reconstruction of an anthropological survey of a post-apocalyptic future California society, complete with accompanying music CD. But I admit it's not for everyone.
For a nice intro to her various styles and themes of writing, I recommend her short story collection A Fisherman of the Inland Sea, which is a fairly broad representative sampler of the sort of thing she writes about in greater detail, including an Ekumen tale set in one of her major universes. It's relatively recent, so should hopefully be fairly easy to find at least on library shelves.
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