A practically applicable strategy is developed to rationally immobilize easily accessed and highly dispersed redox-active metal oxides into porous metal silica (PMS) materials templated and functionalized by porous metal-ligand moieties. On the basis of this strategy, the highly active porous catalyst PMS-1 is successfully targeted for aerobic oxidation of cyclohexane with conversion up to 14.6%, which is much superior to the current industrially adopted catalysts (less than 4% cyclohexane conversion) that use harsh conditions. This promising approach to explore highly active heterogeneous catalysts for inert C-H bond activation should lead to the further discovery of numerous industrially useful catalysts for the oxidation of inert hydrocarbon raw materials.