A novel yolk/shell Fe3O4-polydopamine-graphene-Pt (Fe3O4@PDA/RGO/Pt) nanocomposite is synthesized using polydopamine as a moderate modifier for graphene as well as a coupling agent for the assembly of Pt nanoparticles. The morphology and structure of the as-prepared catalysts are characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy. The detailed formation mechanism of such yolk/shell nanocomposite is discussed. Subsequently, its catalytic activity towards the methanol oxidation is evaluated by cyclic voltammetry, chronoamperometry, electrochemical impedance spectra and CO-stripping voltammetry. Results show that such york/shell Fe3O4@PDA/RGO/Pt exhibits higher electrochemical activity and stability to methanol oxidation than Pt/graphene, which is not only attributed to the synergetic cocatalytic effect at the heterojunction interfaces between the Pt nanoparticles and the support, but also due to the high immobilization of Pt nanoparticles by the functional groups of polydopamine. In addition, the separation ability of Pt nanoparticles from the nanocomposite by Fe3O4 can decrease the CO poison from free Pt nanoparticles. Therefore, this unique yolk/shell nanocomposite may be suitable for the production of catalysts with low-cost and high activity. (C) 2013 Elsevier B.V. All rights reserved.