Electronic structures of the vanadium/vanadium-oxide films supported on alpha-Fe2O3(0001) were studied by using X-ray photoemission spectroscopy. The vanadium films were grown by evaporation of metallic vanadium at room temperature. The as-deposited V had a 3+ oxidation state and the alpha-Fe2O3(0001) surface was reduced at the initial coverage. After complete reduction of interface iron atoms, metallic V started to grow at a vanadium coverage greater than 2/3 monolayer. The V2O5 film was prepared by exposing the pre-deposited vanadium film to the atomic oxygen at room temperature. Converting to the V2O5 film was accompanied by re-oxidation of the alpha-Fe2O3 at the interface. The reduction and reoxidation of interfacial iron manifest electron transfer between the adsorbed vanadium and substrate. (c) 2006 Elsevier B.V. All rights reserved.