An uncommon mixed-valence (+V/+IV) vanadium oxide with a layered-structure was prepared by a sol gel process, starting from a novel vanadium(IV) alkoxide, [{V(OPri)(3)}(2) (p-OPri)(2)]. The obtained product was characterized by FT-IR, Raman spectroscopy, X-ray diffractometry, UV-Vis spectroscopy and EPR. The results indicate that it has a bariandite-like structure and a V10O24 center dot 9H(2)O stoichiometry. Preliminary studies showed that this mixed-valence vanadium oxide has a good lithium intercalation capacity with make it a potential candidate to be used as cathode in lithium-based batteries. (C) 2007 Elsevier B.V. All rights reserved.