Mesostructured cellular foam (MCF) silica was synthesized via surfactant templating route. The surface of MCF silica was then modified by grafting 3-aminopropyl-triethoxysilane (APTES) to have the positive charge, and thus, to provide sites for the immobilization of H3PMo12O40 (PMo12). By taking advantage of the overall negative charge of [PMo12O40]3-, PMo12 catalyst was chemically immobilized on the amine-functional group of surface modified MCF (SM-MCF) silica as a charge matching component. It was found that pore structure of MCF silica was maintained even after the surface modification and the subsequent immobilization of PMo12. It was also revealed that PMo12 species were finely and molecularly dispersed on the SM-MCF silica via chemical immobilization.