Pyridylporphyrin (PyP) was synchronously synthesized and immobilized on the surfaces of crosslinked polystyrene microspheres (CPS microspheres) via an Adler reaction between solid-liquid phases, resulting in PyP-immobilized microspheres, PyP-CPS microspheres. Then the cationic porphyrin-immobilized microspheres, MPyP-CPS microspheres ("M" represents methyl group that comes from iodomethane), was prepared via the quaternization reaction of PyP-CPS microspheres with iodomethane as reagent. In the current work, the efficiency of the above route to immobilize pyridylporphyrin PyP on CPS microspheres was first researched by a comparison method, and then the multi-functionality of the cationic porphyrin-immobilized microspheres MPyP-CPS were mainly tested and examined from many aspects. The investigation results show that: (1) the above route to immobilize pyridylporphyrin on the surfaces of CPS microspheres is highly efficient, and the immobilization amount of PyP on CPS microspheres can get up to about 0.2 mmol g(-1); (2) the cationic porphyrin-immobilized microspheres MPyP-CPS are a kind of multifunctional polymeric microspheres because of their special surface structure, and they can be used to construct different host-guest systems, resulting in many applications. MPyP-CPS microspheres can used as triphase-transfer catalysis in organic synthesis, can coordinate to transition metal ion to form immobilized metalloporphyrin catalysts to be used in the green catalytic oxidations, can be used as support of heteropoly acid to prepare heterogenous heteropoly acid catalyst, and MPyP-CPS microspheres also can used as solid adsorbent in the removal of toxic chromate ion from water medium. In a word, the polymeric microspheres supporting cationic porphyrin. MPyP-CPS microspheres, will have vast application prospect in various fields because they have special surface chemical structure. (c) 2012 Elsevier B.V. All rights reserved.