Ordered mesoporous carbon–silica composites, were synthesized via direct-templating method using soluble phenolic resins as carbon sources, tetrabutyl orthosilicate as SiO2 precursors and triblock copolymer F127 as the structure-directing agent. The structure and the corresponding electrocatalytic activity of carbon–silica composites with various silica contents are systematically investigated. Textual characterization results show that the ordered mesoporous structure of carbon–silica composite with trace SiO2 is well preserved. The electrochemical properties of the supported catalysts were studied by cyclic voltammogram, revealing that ordered mesoporous carbon–silica composites as the support possess excellent electrochemical performance for hydrogen oxidation. The electrochemical active surface area of carbon–silica supported Pt nanoparticles can achieve 63.8m2/g, which is about 7-fold that of non-silica supported Pt catalyst.