This paper describes a new method for preparing lithiated vanadium oxides which are suitable as the cathode material for secondary lithium batteries. Characterization by powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) shows that these oxides are somewhat structurally different from LiV3O8 prepared by the solid-state reaction route, although the starting materials are identical in both cases. The discharge capacity of the oxide is much higher than that of crystalline LiV3O8, and can attain 250 mAh g(-1) at the current density of 0.2 mA cm(-2). The specific capacity and the cycling behaviour of these lithiated vanadium oxides are closely related to post-synthesis heat treatment. This suggests that the amount of water bound to the structure determines electrochemical performance of the oxide in secondary lithium batteries.