TiO(2) nanoparticles-decorated graphene nanosheets have been prepared by a facile hydrothermal method. After depositing Pt nanoparticles exclusively around the interface between TiO(2) and rGO, the obtained Pt/TiO(2)@rGO electrocatalyst exhibits remarkably enhanced electrocatalytic performance, which could be attributed to the unique structure and some possible synergetic effect from the 3-phase Pt-TiO(2)-rGO junctions.