We studied the electronic structure of a chemically Li-intercalated V2O5 xerogel. The technique used in the study was V 2p and O 1s X-ray absorption spectroscopy (XAS). The V ions in the as-prepared V2O5 xerogel are mostly in a pentavalent V5(+) state. The spectra show that the V ions are partially reduced to V4(+) and V3(+) states upon Li intercalation. The results also show that low Li intercalation (x 1), this mechanism saturates and leads to Li,O formation.