Monodisperse crosslinked poly(hydroxyethyl methacrylate) particles (pHEMA) were synthesized for immobilization of the chiral Mn(III)salen homogeneous catalyst by axial coordination. The pHEMA-Mn(III)salen catalyst was subsequently characterized by FT-IR, UV and scanning electron microscopy. The results showed that, the heterogeneous Mn(III)salen catalysts also exhibited high activity and enantioselectivity compared to the homogeneous catalyst for the disubstituted cyclic indene and 6-cyano-2,2-dimethylchromene. Moreover, the catalysts were easily separated from the reaction systems and could be renewed several times without significant loss of catalytic activity. Meanwhile, the enantiomeric excess (ee) value remained at 80% in the eighth cycle. The pHEMA support, immobilized by Mn(III)salen, probably acted as a mediator of the reaction between the substrate and the oxidant, and enhanced the stability of the Mn(III)salen compound.