The surface termination and the nominal valence states for hexagonal LuFeO3 thin films grown on Al2O3(0 0 0 1) substrates were characterized by angle resolved x-ray photoemission spectroscopy. The Lu 4f, Fe 2p and O 1s core level spectra indicate that both the surface termination and the nominal valence depend on surface preparation, but the stable surface terminates in a Fe-O layer. This is consistent with the results of density functional calculations which predict that the Fe-O termination of LuFeO3(0 0 0 1) surface is energetically favorable and stable over a broad range of temperatures and oxygen partial pressures when it is reconstructed to eliminate surface polarity.