Sulfur-doped TiO(2)/Ti photoelectrodes were prepared by anodization and characterized by SEM, AFM, XRD, XPS, UV-vis and SPS. The results of investigation indicated that S(4+) and S(6+) were dispersed on the surface of TiO(2) nanoparticles. The doping with an appropriate amount of sulfur expanded the response range of TiO(2)/Ti photoelectrodes to visible light, and enhanced the separation of photoinduced electrons from cavities. The photoelectrocatalytic performance test run with sulfur-doped TiO(2)/Ti photoelectrodes under Xenon light indicated that Na(2)SO(3) concentration of 750 mg/L and voltage of 160 V were the optimal conditions for preparation of sulfur-doped TiO(2)/Ti photoelectrodes.