Mesoporous carbon microfibers (MCMFs) were prepared using one-dimensional alumina microfibers as the templates via chemical vapor deposition method. Physical adsorption of nitrogen, X-ray diffraction, thermogravimetric analysis, field-emission transmission electron microscopy, energy dispersive X-ray analysis, and field-ernission scanning electron microscopy techniques were used to study the structure and morphology of the samples. MCMFs possess a core/shell structure with a surface area of 409 m(2)/g. The core structure of the obtained MCMFs was composed of mesopores with a pore size of 8.8 nm, whereas the dense shell with a thickness of around 15-20 nm was built up with roughly parallel discrete graphene layers. Compared with Pt catalyst supported on Vulcan XC-72, catalyst supported on MCMFs displayed a better CO tolerance and catalytic activity in electrooxidation of methanol at room temperature.