In the current work, TiO2 nanotube array was prepared via electrochemical anode method. Then the Bi2O3 nanoparticles were deposited onto the TiO2 nanotube array via dip-coating method from an amorphous complex precursor. The crystal structures were characterized via X-ray diffraction analysis. Their surface textures were observed via electron-scanning microscope. The prepared composite array electrode exhibited high photoelectrocatalytic activities towards degrading organic contaminants under visible light irradiation. High photoelectrocatalytic activities were also exhibited under UV light irradiation. The catalytic mechanism was discussed based on the analysis of electrochemical and degradation kinetics results. It is suggested a P (Bi2O3)-N (TiO2) junction was formed to increase the catalytic activates. The stability of the electrode materials was confirmed finally. (C) 2011 Elsevier B.V. All rights reserved.