Vanadium oxide films were prepared via the sol–gel process and dip coating method, using V2O5as raw materials and H2O2(volume fraction 30) as the solvent. Mn and Ni ions were added to vanadium oxide sol to prepare doping vanadium oxide films. The films were characterized by atomic force microscopy, FT-IR, X-ray diffraction and electrochemical techniques. The add-on of Metal ions will not affect the morphology of the vanadium oxide films, but change the valence of vanadium ion and vanadium oxide crystal phase. Furthermore, cyclic voltammetry curves show that metal ions doping vanadium oxide films exhibit reversible electrochemical reaction. But electrochemical impedance spectroscopy indicates pure vanadium oxide film has a better diffusion rate.