The photocatalytic activity composite films incorporating the Keggin-type polyoxometalates (POM) K6CoW12O40 center dot 16H(2)O and K3PW12O40 center dot nH(2)O (MW12 (M = P, Co)) and [Cu(II)(1,8-dimethyl-1, 3, 6, 8, 10, 13-hexaazacycloteradecane)](2+)(L) have been prepared by the layer-by-layer (LbL) self-assembly method. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. Atomic force microscopy (AFM) images of the L/MW12 composite films indicate that the film surface is relatively uniform and smooth. In addition, the films show high photocatalytic activity to the degradation of organic dye model (methyl orange (MO)), attributed to the formation of an O -> W charge-transfer excited state at W-O-W bridge bond, resulting in generating highly reactive holes and electrons; The photocatalytic efficiency of the films have little change after several times of photocatalytic cycle, indicating that the composite films are stable, reused and recovered. (C) 2009 Elsevier Inc. All rights reserved.