A novel and simple preparation method for preparing a mesocellular carbon foam (MCF-C) is described. A silica–polymer composite as an amphi-templating material was synthesized by a sol–gel method using tetraethyoxy-orthosilicate (TEOS), P123 and divinylbezene (DVB) as a silica precursor, a template and a polymer precursor, respectively. The silica–polymer composite was subsequently transformed to either mesocellular carbon foam (MCF-C) or mesocellular silica foam (MCF-S). The prepared MCF-C exhibited well-developed mesocell pore structures with uniform windows. Compared to conventional methods, the method used for preparing MCF-C was economical and simple. MCF-C was used as a catalyst support in methanol electro-oxidation. The Pt/MCF-C-ETX (MCF-C-supported Pt catalyst which was prepared using sodium ethoxide) catalyst has smaller Pt nanoparticles and a larger electrochemically active surface area (EAS) value than the commercial Pt/C catalyst. In methanol electro-oxidation, the prepared Pt/MCF-C-ETX catalyst showed a higher catalytic performance than the commercial Pt/C catalyst.