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α′-NaV2O5 transforms at TC = 34 K, and the origin of the phase transition seems to be caused by the charge order and spin-Peierls mechanism. However the experiments which reveal the existence of charge order are very little. We measured XANES of V atoms which relates to the valence of V. It was found that the valences of V atoms in NaV2O5 were V4.5+ in the high temperature phase by comparing pre-edge and XANES of NaV2O5 with that of LiV$_2O5, CaV2O5 and V2O5. The analysis of EXAFS also shows the environment of the V4.5+ state.

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