Two silsesquioxane-based hybrid porous polymers (PcsM and PcsH) were easily synthesized by the Friedel−Crafts reaction of tetraphenylporphyrin derivative (HTPP and MnTPP) with octavinylsilsesquioxane (OVS) applying AlCl 3 as catalyst. A series of characterization results demonstrate that the materials have been successfully prepared. PcsM and PcsH act as effective catalysts to selectively oxidize styrene to styrene oxide with oxygen as a green and economical oxidant. The effects of reaction conditions on the reaction activity, such as reaction energy, reaction time, solvent type, catalyst dosage, etc., were systematically discussed. Under optimized conditions, the conversion rate of styrene was 99.9%, and the yield of styrene oxide could reach 80.6%. Moreover, the reaction mechanism of selective oxidation of styrene to styrene oxide using PcsM as a catalyst is reasonably proposed. Importantly, PcsM shows an excellent recyclable performance.