A kind of graphene nanosheets (GNSs) supported hollow composite of Pt and CoSn(OH)6 electro-catalyst (H-Pt&CoSn(OH)6/GNSs) is prepared using cobalt metal nanoparticles as sacrificial templates. Transmission electron microscope measurements show that GNSs supported H-Pt&CoSn(OH)6 nanospheres are coreless with a uniform particle size of 11nm. Electrochemical measurements demonstrate that the H-Pt&CoSn(OH)6/GNSs electro-catalyst exhibits enhanced electro-catalytic performance for methanol oxidation compared with solid Pt&CoSn(OH)6/GNSs, and Pt/GNSs catalysts.