Vanadium pentoxide aerogels are pillared nanocomposites with exceptional stability, intercalation capacity, and reversibility. X-ray absorption spectroscopy (XAS) measurements on pristine and doped materials have revealed details of the oxidation state and local structure of the host material and of the polyvalent doping species. XANES measurements at the Cu K-edge for Cu-0.1 V2O5 show the atomic level reversibility of the structure upon Li+ insertion/release cycling.