The use of sol-gel processes in the preparation of cathode materials is of growing interest because of their ease and flexibility. The electrochemical properties, e.g. the rate of lithium intercalation, appear to depend on the morphology of the thin-film vanadium oxide xerogels that can be changed by modifying the preparation. In this context, in order to extend the study to bulk materials, xerogel powder samples with surface areas in the range 2-5 m(2)/g have been prepared from pure vanadium pentoxide hydrogels, or in the form of composites, from carbon powder added to hydrogels. The electrochemical properties have been correlated with the morphological and structural changes induced by the presence of carbon using X-ray and XAS spectroscopy.