The development of semiconductor-based photoelectrocatalysts with superior activity is of great importance for water purification. Here, we fabricated graphene oxide (GO)-wrapped Ti/PbO2 photoanodes by combination of electrochemical deposition and electrophoretic deposition process. The as-obtained composite electrodes showed better performance for photoelectrocatalytic (PEC) degradation of reactive brilliant blue KN-R, as compared with that of Ti/PbO2 reference. Experimental results demonstrated that the efficient PEC performance of graphene oxide (GO)-wrapped Ti/PbO2 photoanodes could be ascribed to the low charge transfer resistance, large electrochemical active areas, and high separation efficiency of induced electrons/holes. Furthermore, a significant photoelectric synergy effect can be observed for the graphene oxide (GO)-wrapped Ti/PbO2 photoanodes during the photoelectrocatalytic process.