Here, we report a novel method for assembling reduced graphene oxide (RGO) and Pt nanoparticles on a carbon fiber (CF) electrode successively to form a stable Pt nanoparticle-RGO-Pt nanoparticle-RGO/CF multiple junction for electrocatalysis application. As the SEM imaging exhibited, Pt nanoparticles are uniformly deposited on the surface of each RGO sheet, performing an alternative covering structure of RGO and Pt nanoparticle multi-layer on the CF electrode. Thus, a novel three-dimensional (3D) multi-layered Pt/RGO modified CF electrode (N-Pt/RGO/CF) is obtained. Experimental results demonstrate that the prepared N-Pt/RGO/CF electrode shows good electrochemical properties and enhanced electrocatalytic activity toward methanol electrooxidation in alkaline medium as compared with the Pt/RGO/CF electrode without layer-by-layer structure or the Pt/CF electrode without RGO. It is due to the unique 3D pore structure of N-Pt/RGO/CF and the good electron transport property of RGO in the composite electrode. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.