The disadvantages of high cost, easy poisoning and insufficient durability hinder platinum (Pt) application in direct methanol fuel cells. In this study, a hybrid of reduced graphene oxide/carbon nanotubes-supported hollow copper spheres (Cu/rGO@CNTs) is prepared by a one-step electrodeposition method. Then, the internal and external surfaces of hollow Cu spheres are coated with Pt skims to obtain a hollow bimetallic electrocatalyst (Pt/Cu/rGO@CNTs) through a simple galvanic replacement reaction by immersing Cu/rGO@CNTs in a chloroplatinic acid (H2PtCl6) solution. The three dimensional rGO@CNTs network structure benefit mass transport and electron transfer. Pt skims expose abundant active sites for electrocatalytic methanol oxidation reactions (MORs). Cu cores synergize Pt skims to enhance anti-poison ability. As a result, Pt/Cu/rGO@CNTs shows an excellent electrocatalytic activity for MORs with a robust tolerance of catalyst poisoning. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.