The electronic structure of V2O5 has been studied by resonant photoemission spectroscopy (RPES) and band structure calculation. The RPES data showed that the valence band (VB) of V2O5 is formed by strong hybridization of O2p and V3d states, the contribution from V3d state is predominant in the high binding energy (BE) region of the VB. The approximate charge distributions of O and V ions in V2O5 are calculated for the first time as V23+O51.2- from the RPES data. (c) 2006 Elsevier B.V. All rights reserved.