Vanadium pentoxide materials prepared through sol-gel processes act as excellent intercalation hosts for lithium as well as for polyvalent cations. Previous ex situ X-ray absorption spectroscopy and X-ray diffraction characterizations have shown that the electrochemical performance of vanadium pentoxide xerogels depends inversely on the long-range order of the V2O5-layered structure. Recently, new ways to prevent the self-organization of the dry materials, which takes place upon water removal from the starting hydrogel, have been introduced. In the present paper we report on the in situ X-ray absorption spectroscopy characterization of a spray-coated V2O5 (freeze-dried) xerogel cathode upon lithium intercalation.