XPS measurements have been performed on the orthogonal single phase YBa2Cu3O7 superconductor. The higher valence-like state of Cu is observed clearly. The electronic states corresponding to the peaks in Cu2p and O1s XPS are discussed. It is suggested that the extra holes due to the excess oxygen are created on the O2p orbit. The higher valence-like state of Cu corresponds to the combination of Cu3d9L and Cu3d10L3 states.