In order to produce thin films of crystalline V2O5, vanadium metal was thermally oxidised at 500°C under oxygen pressures between 250 and 1000mbar for 1–5min. The oxide films were characterised by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). The lithium intercalation performance of the oxide films was investigated by cyclic voltammetry (CV), chronopotentiometry and electrochemical impedance spectroscopy (EIS). It was shown that the composition, the crystallinity and the related lithium intercalation properties of the thin oxide films were critically dependent on the oxidation conditions. The formation of crystalline V2O5 films was stimulated by higher oxygen pressure and longer oxidation time. Exposure for 5min at 750mbar O2 at 500°C resulted in a surface oxide film composed of V2O5, and consisting of crystallites up to 200nm in lateral size. The thickness of the layer was about 100nm. This V2O5 oxide film was found to have good cycling performance in a potential window between 3.8 and 2.8V, with a stable capacity of 117±10mAh/g at an applied current density of 3.4μA/cm2. The diffusion coefficients corresponding to the two plateaus at 3.4 and 3.2V were determined from the impedance measurements to (5.2 and 3.0)×10−13 cm2 s−1, respectively. Beneath the V2O5 layer, lower oxides (mainly VO2) were found close to the metal. At lower oxygen pressure and shorter exposure times, the oxide films were less crystalline and the amount of V4+ increased in the surface oxide film, as revealed by XPS. At intermediate oxygen pressures and exposure times a mixture of crystalline V2O5 and V6O13 was found in the oxide film.