We have investigated thin films containing nanosized grains of V2O5, new V/Ce oxides, Fe2O3 and V2O5, V/Ce, and Fe2O3, with Li by the thermally stimulated currents, impedance spectroscopy, Raman spectroscopy, and grazing-incidence small-angle X-ray scattering (GI-SAXS) at the Elettra Synchrotron (Italy, Trieste). Combining different experimental methods, the dependence of structural and electrical properties upon percentage of Li added into the matrix of these metal-oxide films was found. These changes are explained by the structural changes of grains (and grain boundaries) and with the impact of Li+ ions in the charge transfers. The average grain radius < R >, obtained by GI-SAXS, increased in V/Ce oxide at 38 atoms % V upon the intercalation of Li+ ions. This particular morphology is quite suitable for application in electrochromic devices in an advanced electrochemical cell concept and efficient new solar cells. (c) 2005 The Electrochemical Society.