Nitrogen-containing mesostructured cellular foam carbon (N-MCF-C) was synthesized by a templating method using mesostructured cellular foam silica (MCF-S) and polypyrrole as a templating agent and a carbon precursor, respectively. The N-MCF-C was then modified to have a positive charge, and thus, to provide a site for the immobilization of [PMo 10 V 2 O 40 ] 5− . By taking advantage of the overall negative charge of [PMo 10 V 2 O 40 ] 5− , H 5 PMo 10 V 2 O 40 (PMo 10 V 2 ) catalyst was chemically immobilized on the N-MCF-C support as a charge-matching component. Characterization results showed that the PMo 10 V 2 catalyst was finely dispersed on the N-MCF-C support via strong chemical interaction, and that the pore structure of N-MCF-C was still maintained even after the immobilization of PMo 10 V 2 . In the vapor-phase oxidation of benzyl alcohol, the PMo 10 V 2 /N-MCF-C catalyst showed a higher conversion and a higher oxidation activity (formation of benzaldehyde) than the unsupported PMo 10 V 2 and PMo 10 V 2 /MCF-S catalysts.