The composite material of polyaniline (PANI)/layered manganese oxide film electrode was prepared by the layer-by-layer adsorption technique. The corresponding photoelectrocatalytic activity was studied for the degradation of Rhodamine B (RhB) under visible light irradiation (lambda>400 nm). The efficiency of the self-assembled film to assist photodegradation of RhB improved significantly with an applied potential of 0.9 V vs. standard calomel electrode. The results showed that PANI could enhance the efficiency of photon harvesting, and the impressed current could reduce the chance of electron-hole recombination. A synergetic effect was found between PANI and MnO(2). This study proposed an effective material for the photoelectrocatalytic degradation of RhB under visible light irradiation. (C) 2010 Elsevier B.V. All rights reserved.