The Li oxides species formed on Li over-deposited V2O5 thin film surfaces have been studied by using X-ray and UV induced photoelectron spectroscopy (XPS and UPS). The photoelectron spectroscopic data show that the Li over-deposited V2O5 system itself is not stable. Further chemical decomposition reactions are taken place even under UHV conditions and lead to form Li2O and Li2O2 compounds on the surface. The formation of Li2O2 causes to arise an emission line at about 11.3 eV in the valence band spectra. (c) 2004 Elsevier B.V. All rights reserved.