Four composite films consisting of Zn(II) and Cu(II) substituted tungstoborates K-7[BW11O39M(H2O)] (BM11M, M=Zn, Cu) and two bipolar hemicyanines of (E)-1,1'-(propane-1,3-diy1)bis(4-(4-(dimethylamino)styryl)pyridinium) bromide ((HBr2)-Br-3) and (E)-1,1'-(decane-1,10-diyl)bis(4-(4-(dimethylamino) styryl)pyridinium) bromide ((HBr2)-Br-10), were prepared by electrostatic layer-by-layer self-assembly technique. These films of (BW11M/H-a)(n) (M=Zn, Cu; a =3, 10) exhibited ultraviolet-visible characteristic absorption bands of BW11M and (HBr2)-Br-a with their absorption intensities increasing linearly with increasing the layer number n, indicating that the composite films were successfully and uniformly deposited. With respect to the (HBr2)-Br-3 and (HBr2)-Br-10 aqueous solutions, the intramolecular charge transfer absorption bands of (HBr2)-Br-3 and (HBr2)-Br-10 in the films exhibited bathochromic shifts to different extents depending on the hemicyanines and BW11M in the films. These films could generate stable, cathodic photocurrents with photocurrent action spectra being consistent with corresponding absorption spectra of the hemicyanines in the films, when illuminated with 100 mW/cm(2) polychromatic light (730 nm > lambda> 325 nm). The effects of the alkyl chain length, BW11M, layer number of the (BW11M/H-a)(n) films, and applied bias potential and electron acceptor in the electrolyte solution on the photocurrent densities are discussed. (C) 2017 Elsevier Ltd. All rights reserved.