Lithium vanadium oxides have been prepared by the direct reaction of an aqueous hydrogen peroxide solution with lithium and vanadium alkoxides, LiO-n-C3H7 and VO(O-i-C3H7)3. The γ-like phase oxide can be obtained at the nominal lithium content x n =3 almost as a single phase. From the thermogravimetric (TG) measurement, it was revealed that the γ-like phase oxide contained water and organic compounds, and the water content n in Li x V2O5·nH2O was found to be about 2.4 for γ-like phase oxide. Water content of the γ-like phase oxides, controlled by heat-treatment at various temperatures, affects charge and discharge behaviours markedly. It should be noted that the average potential of Li2.2V2O5·nH2O is at least 1V higher than that of γ-LiV2O5.