Vanadium pentoxide films were prepared by pulsed laser deposition (PLD) and their surface structure evolution in relation to the growth temperature and as a function of lithium intercalation was studied. The deposition was made onto various substrate materials over a wide substrate temperature range of 30-500 °C, keeping the oxygen partial pressure at 100 mTorr. The surface properties of V2O5 films were studied by Raman scattering spectroscopy in order to understand the effect of substrate temperature on the structure and growth behavior. The results indicated that the structure of PLD V2O5 films is highly dependent on the growth temperature. The Raman spectra provide additional insight into the nature of the structural changes of lithiated films, showing the appearance of the - and -phases of LixV2O5.