Molybdenum doped vanadium pentoxide (Mo doped V2O5) films are prepared by cathodic electrodeposition on indium tin oxide substrate from Mo doped V2O5 sol. As an anodic and cathodic coloration electrochromic material, the electrodeposited Mo doped V2O5 film presents a better cycling stability, reversibility and multi-electrochromic behavior (orange-V2O5-green-blue) with an optical modulation of 60-90% in the spectral region 550-900 nm, which can be expected as a result of enhanced electron intervalence transfer between Mo6+ and Vs+, V4+ states, in addition to V5+ and V4+ transition. The electrochromic mechanism of Mo doped V2O5 films is investigated with atomic force microscopy. X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The surface roughness of the film increase at the different coloration states due to the increasing crystallinity degree. The change of the interlayer spacing for the host V2O5 and the change of the C and Li element states verify the insertion of organic solvent into the interlayer of the host V2O5 and some of the Li+ ions into the sites in the V-O layers. The electrochromic kinetics process indicates that the electrochromism of Mo doped V2O5 films can be considered as a reversible reduction/oxidation process accompanying the insertion/extraction of Li+ ions and electrons. Crown Copyright (C) 2010 Published by Elsevier Ltd. All rights reserved.