TiO₂ nanoparticles-decorated graphene nanosheets have been prepared by a facile hydrothermal method. After depositing Pt nanoparticles exclusively around the interface between TiO₂ and rGO, the obtained Pt/TiO₂@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–TiO₂–rGO junctions.