Nanostructured cobalt vanadium oxide (V2O5) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH2)(6)(2+) cations and the (H2V10O28)(4-) anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V2O5 gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V2O5. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed.