Lithiated Vanadium oxides with polyelectrochromic behaviour are here reported for the first time. The electrochrome was obtained by means of a simple and solvent-free solid state reaction. Clear XPS evidences indicate that the electro-generation of red color is due to the dismutation of surface-adsorbed O2- species with subsequent formation of red colored V5+-O22- complexes. The reaction is switched electrochemically by oxidation of the surface V4+ centers.