Nitrogen-rich macroporous carbon (N-MC) was prepared using melamine-formaldehyde resin as a carbon precursor. The surface of N-MC was then modified to have a nitrogen-derived functional group (amine group), and thus, to provide an anchoring site for heteropolyacid (HPA) catalyst. By taking advantage of the overall negative charge of [PMo10V2O40](5-), H5PMo10V2O40 (PMo10V2) HPA catalyst was chemically immobilized on the N-MC support as a charge matching component. It was found that PMo10V2 was finely dispersed on the N-MC support. In the model vapor-phase 2-propanol conversion reaction, the PMo10V2/N-MC catalyst showed a remarkably enhanced oxidation catalytic activity and a suppressed acid catalytic activity compared to the mother catalyst. The PMo10V2/N-MC catalyst served as an efficient oxidation catalyst in the reaction where both acid and oxidation reactions occurred simultaneously.