A novel route to make crosslinked polystyrene (CPS) microspheres to be porphyrin-functionalized via two special polymer reactions, Kornblum reaction and Adler reaction, was designed and founded. The chloromethyl groups of chloromethylated crosslinked polystyrene (CMCPS) microspheres were first oxidized to aldehyde groups by dimethyl sulfoxide as oxidant via Kornblum oxidation reaction, obtaining aldehyde group-modified microspheres, ALCPS microspheres, in which, a great quantity of benzaldehyde groups suspend from the main chain, and the effects of the main factors including the reaction temperature, the addition of KI as catalyst and the used amount of NaHCO 3 as acid acceptor on the oxidation reaction were examined. Subsequently, the synchronic synthesizing and immobilizing of porphyrins on CPS microspheres were carried out via the Adler reaction between solid and liquid phases, in which, ALCPS microspheres, pyrrole and benzaldehyde or benzaldehyde analog in a solution were used as co-reactants, resulting in porphyrin-functionalized microspheres, and the influence of diverse factors including the acidity of the protonic acid catalyst, the substituent structure of benzaldehyde analog, and the polarity of the solvent as well as the swelling property of the solvent for CPS microspheres on the process of synchronously synthesizing and immobilizing porphyrins on CPS microspheres were investigated in depth. The experimental results indicate that via the designed route, the porphyrin-functionalization of CPS microspheres can successfully be realized. For the Kornblum oxidation reaction, under the optimal reaction conditions, the conversion of chloromethyl groups can reach 90%. For the Adler reaction between solid and liquid phases, the fitting protonic acid catalyst is lactic acid, appropriate solvent is a mixture of dimethyl sulfoxide and xylene, and using 4-chlorobenzaldehyde as a benzaldehyde analog reactant in the solution is in favor of the porphyrin-functionalization of CPS microspheres. Under these specific conditions, the immobilized amount of porphyrin can get up to 23.33 mmol/100 g.