@[email protected] I'm a big fan of reading short stories before committing to books I don't know yet. So, my recommendation are either of her short story compilations: The Wind's Twelve Quarters, or Changing Planes.
TWTQ is a smattered sampling, stories taking place in different universes, written at different periods of her life.
Changing Planes is composed of vignetttes on the same prompt - if visiting different planes of existence was accessible, who would you encounter?