Porous carbon materials (SM-C, HS-C and TM-C) were prepared using commercial colloidal silicas (SM-30, HS-40 and TM-50) and a resorcinol-formaldehyde resin as a removable template and a carbon precursor, respectively. All of the prepared carbons had high surface areas with narrow pore size distributions. In particular, the pore diameter of the carbons could be controlled over a range of mesopore size by the use of an appropriate silica employed as a template. Mesoporous carbon templated using TM-50 had the largest pore size, while that for SM-C, was the smallest. Pt nanoparticles were supported on these mesoporous carbons for use as a catalyst in a polymer electrolyte membrane fuel cell (PEMFC). The crystallite size of the Pt catalyst was found to be closely related to the properties of the corresponding carbon support. A carbon support with a large pore size and a high surface roughness was found to favor the dispersion of Pt crystallite. In a single cell test, the Pt catalysts supported on mesoporous carbons exhibited higher cell performance than that on activated carbon. In particular, the Pt/TM-C catalyst showed the best cell performance among the catalysts tested. In addition to the high surface area of the active metal, the large pore size of the Pt/TM-C appears to have positive effect on the distribution of ionomer, resulting in facile formation of a triple-phase boundary.