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The V2O5 sol was fabricated by ultra-fast quenching.The vanadium with low valence (V4+) was found in V2O5 xerogel films by XPS analysis.The technology of oxygen top-blown was applied to analyze the XPS spectrum difference of V2O5 xerogel when the powder of V2O5 was melting in air or in oxygen atmosphere.The results show that the different melting atmosphere has certain influences on the chemical valence of V2O5 xerogel.