The photoelectrochemical degradation of methylene blue in aqueous solution was investigated with three-dimensional electrode-photocatalytic reactor. It was found that the methylene blue could be degraded more efficiently by photoelectrochemical process than by photocatalytic oxidation or electrochemical oxidation alone. The decolorization efficiency and COD reduction were 95% and 87% for a photoelectrochemical process, respectively, while they were only 78% and 68% for a single electrochemical process and 89% and 71% for a single photochemical process. The TOC reduction of the former also reached as high as about 81% within a reaction time of 30.0 min. And these degradation reactions conformed to pseudo-first-order kinetics.