Sulfur-doped TiO2/Ti photoelectrodes were prepared by anodization and characterized by SEM, AFM, XRD, XPS, UV-vis and SPS. The results of investigation indicated that S4+ and S6+ were dispersed on the surface of TiO2 nanoparticles. The doping with an appropriate amount of sulfur expanded the response range of TiO2/Ti photoelectrodes to visible light, and enhanced the separation of photoinduced electrons from cavities. The photoelectrocatalytic performance test run with sulfur-doped TiO2/Ti photoelectrodes under Xenon light indicated that Na2SO3 concentration of 750 mg/L and voltage of 160 V were the optimal conditions for preparation of sulfur-doped TiO2/Ti photoelectrodes. (C) 2008 Elsevier B.V. All rights reserved.