The practical application of low temperature fuel cells is largely hindered by the unavailability of efficient electrocatalysts with high activity and stability. A promising strategy to design highly active electrocatalysts is to use multicomponent catalysts including alloyed active metals and metal oxides as the support. In this paper, we develop highly efficient and stable sandwich-structured TiO2–Pt–G(graphene) hybrid electrocatalysts. Structural characterization and electrochemical measurements indicate that these TiO2–Pt–G hybrid electrocatalysts have much higher activity and stability compared to conventional carbon black supported Pt electrocatalysts. The significantly enhanced electrochemical performance is ascribed to the unique sandwich sheet-like structure that is responsible for the strong metal–support interaction and the proposed synergetic effect. These findings suggest that such TiO2–Pt–G hybrid electrocatalysts are promising for use in low temperature fuel cells.