Three kinds of new electrostatic self-assembled multilayer films were prepared with alternating adsorption of H3PMo12O40 and hemicyanine derivatives,and characterized with UV-visible absorption spectroscopy and cyclic voltammetry.The results show that these films are vertically uniform and electrochemically active with surface-controlled behavior,and the charge transfer may occur between H3PMo12O40 and hemicyanine derivatives in the films.The electron transfer rates of the three films are derived to be 0.0027,0.0019 and 0.00066 s-1,respectively,which decrease with increasing the thickness of the hemicyanine layers in the films.