A photoelectric conversion film consisting of sandwich-type tetracadmium(II) tungstophosphorate [P2W18Cd4(H2O)(2)O-68](10-) ((PW18Cd4)-W-2) and a bichromophore hemicyanine of (E)-1,1'-(hexane-1,6-diyl)bis(4((E)-2-(4-(dimethylamino)naphthalen-1-yl)vinyl)pyridinium) bromide (N-6) was prepared by electrostatic self-assembly technique, and characterized by UV-vis spectroscopy, cyclic voltammetry and photoelectrochemistry. The UV-visible spectra showed that the film was uniformly deposited and N-6 molecules formed J-aggregations in the films. The cyclic voltammetry showed that the P2M18Cd4 and N-6 in the films were electrochemically active with surface-confined characteristics. As irradiated with white light, the (P2W18Cd4/N-6) monolayer film gave stable cathodic photocurrent that is 2.4- and 6.7-fold as great as electrostatically self-assembled monolayer film of (P2W18Cd4/H-6) {H-6 = (E)-1,1'-(hexane-1,6-diyl)bis(4-(4-(dimethylamino)styryl)pyridinium) bromide} and Langmuir-Blodgett monolayer film of analogous hemicyanine (E)-4-(2-(4-(dimethylamino)naphthalen-1 -yl)vinyl)-1-octadecylpyridinium iodide. The photocurrent action spectrum indicated that the cathodic photocurrent was generated based on charge transfer excitation of the N-6 in the film. The effects of applied bias voltages, electron acceptor, and layer numbers of the (P2W18Cd4/N-6)(n) films on photocurrent generation of (P2W18Cd4/N-6)(n) film were examined. (C) 2013 Elsevier Ltd. All rights reserved.