Noble metal ruthenium-doped TiO2/Ti photoelectrodes were prepared by anodization. The photoelectrodes were characterized by EIS, XRD and SEM. And the photoelectrocatalytic degradation of methylene blue was carried out using the photoelectrodes. The results show that ruthenium doping can increase the specific surface area and enhance the photoelectrocatalytic activity of TiO2/Ti photoelectrodes. In 0.5% HF electrolyte, the optimal parameters are anodization voltage of 20 V, anodization time of 20 min and heat treatment of 600 oC for ruthenium-doped TiO2/Ti photoelectrode preparation. With bias voltage of 0.2 V, methylene blue were decolored completely in 120 min by ruthenium-doped TiO2/Ti photoelectrodes under UV light(125 W).