In this paper, a kind of environmental friendly and cost-effective bamboo charcoal (BC) is used as catalyst support in DMFCs instead of carbon nanotubes (CNTs), which is toxic and expensive. After special treatments, we obtain a sponge-like three-dimensional (3D) BC, which can provide high specific surface area (1264.5 m(2) g(-1)) and porous matrices. Then, tungsten carbide (WC) and Pt are loaded on the BCs with microwave-assisted technique and 3D structural Pt/WC/BCs electro-catalyst is finally fabricated. Subsequently, the catalyst is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the further electrochemical investigation, it was found that Pt/WC/BCs catalyst has higher performance (2.76 mA cm(-2)) and better CO-tolerance for methanol oxidation compared with Pt/WC/CNTs and commercial Pt/C. Herein, we believe that the as-synthesized 3D Pt/WC/BCs catalyst has great promising application in DMFCs. (C) 2013 Elsevier B.V. All rights reserved.