We study the electronic structures of LiMn2O4 by x-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) and resonant photoelectron spectroscopy (RPES). XPS data suggest that the average oxidation state of Mn ions is 3.55, probably due to the small amount of lithium oxides on the surface. UPS and RPES data imply that Mn ions are in a high spin state, and RPES results show strong Mn3d-O2p hybridization in the LiMn2O4 valence band.