Vanadium pentoxide materials prepared through sol–gel processes (xerogel, aerogel and aerogel-like) act as excellent intercalation hosts for lithium as well as for polyvalent cations. The large lithium insertion capacity of these materials makes them attractive for use as cathodes in high capacity lithium batteries. This paper describes the utility of X-Ray absorption spectroscopy (XAS) for the investigation of gel-based V2O5 materials. In particular, X-ray near edge structure (XANES) and polarized EXAFS experiments are highlighted.