Mixed Vanadium oxide/CeO2 films and powders prepared via inorganic sol-gel route were characterized using impedance spectroscopy, grazing-incidence small angle X-ray scattering (GISAXS) and Infrared and Raman spectroscopies. Variation of film resistivity with composition is related to variation of porosity. Grain sizes obtained by GISAXS are compared with the values previously obtained by AFM and XRD. The structure of V/Ce mixed oxides is studied using Infrared and Raman spectroscopies and the results, especially characterization of amorphous phase, are compared with the previously published results obtained using X-ray spectroscopy. (C) 2004 Elsevier B.V. All rights reserved.