Lithium (Li) (0-5 wt%) doped V2O5 thin films were spray deposited at 450 degrees C onto ITO substrates. Structural analysis using X-ray diffraction and Raman spectroscopy revealed orthorhombic phase of the films. In addition to the V2O5 phase, presence of VO2 peaks due to high deposition temperature is also evident from structural and optical characterization. The non-stoichiometric nature of the films due to loss of the terminal O atom was confirmed from Raman spectroscopy. The direct band gap, indirect bandgap, and phonon energies were also calculated from optical studies. Different charge states of vanadium ions present in the film were identified from X-ray photoelectron spectroscopy study. Results from cyclic voltammetry experiments reflected significant differences between the undoped and Li doped V2O5 samples. Transport properties by Hall-effect measured at room temperature indicated significant increase in conductivity, carrier concentration and mobility of V2O5 thin films on doping with Li. A Dye Sensitized Solar Cell (DSSC) was fabricated using mobility enhanced 5 wt% Li doped V2O5 film as photoanode and its efficiency was found to be 2.7%. A simple electrochromic cell is fabricated using undoped V2O5 thin film to demonstrate the colour change. (C) 2015 Elsevier B.V. All rights reserved.