Thin films of orthorhombic V2O5 have been prepared by sol electrophoretic deposition (EPD) followed by post-treatment at 500°C. Their electrochemical and optical performances have been investigated for possible applications in electrochemical/electrochromic devices. Li+-intercalation properties of the films have been explored in two voltage ranges: 0.4 to −1.1V and 0.4 to −1.6V versus Ag/Ag+, respectively. High capacities of over 300mAh/g are acquired in the wider voltage range at a current density of 50μA/cm2 and moderate capacities of 140 and 110mAh/g are obtained in the narrower voltage range at a current density of 25 and 50μA/cm2, respectively. Electrochemical measurements have shown that the films demonstrate good cyclability in both voltage ranges. X-ray diffraction, scanning electron microscopy and optical spectra have been used to examine the changes in crystallinity, microstructure, morphology and transmittance of the films during cycling. Films cycled to a deeper voltage of −1.6V versus Ag/Ag+ deliver higher capacity with appreciable morphological change, while films cycled in the narrower voltage range show moderate capacity and maintain the morphology, optical responses and crystalline structure. Voltage range can be optimized in between to acquire both high capacity and stability in structure, electrochemical and optical properties. High Li+-intercalation capacity and good cyclic stability are attributed to the porous structure of V2O5 films prepared by EPD.