On the basis of synthesis of styrene-hydroxyethyl methacrylate copolymer microspheres with a functionalized hydroxyl, we have prepared a new type of copolymer microspheres immobilized porphyrinatomanganese(III), P(St-co-HEMA)MnP, by a condensation reaction between a hydroxyl in copolymer microspheres surface and a carboxyl in porphyrin ring. The obtained copolymer catalyst (P(St-co-HMEA)MnP) was characterized by SEM, UV-vis, IR, ICP and TG-DTG. The SEM image shows that the morphology of the copolymer catalyst is spheriform with ca. 4 mu m diameter. The catalytic activity of P(St-co-HMEA)MnP to epoxidize cyclohexene in the presence of molecular oxygen and isobutylaldehyde has been studied. The catalytic efficiency of P(St-co-HMEA)MnP is comparable to that of non-supported MnCMPTTP. It is a mild, reusable and highly efficient heterogeneous catalyst for the epoxidation of cyclohexene. (C) 2010 Elsevier B.V. All rights reserved.