Exploiting highly efficient electrocatalysts through simple methods is very critical to the development of energy conversion technologies. Herein, we develop a hierarchical reduced graphene oxide supported dealloyed platinum copper nanoparticle catalyst (Pt-Cu/RGO) by a facile one-step electrodeposition of graphene oxide in the presence of H2PtCl6 and copper ethylenediamine tetraacetate. The nanostructure and composition were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Meanwhile, the electrocatalytic performance was investigated by cyclic voltammetry and chronoamperometry, showing that the Pt-Cu/RGO catalyst not only equips with an outstanding electrocatalytic activity for the methanol oxidation reaction (2.3 times that of commercial Pt/C catalyst), but also shows a robust durability and superior tolerance to CO poisoning. The excellent electrocatalytic performance could be attributed to the three-dimensional hierarchical structure, porous dealloyed nanoparticles and synergistic effect between each component. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.