A series of chiral salen Mn(III) catalysts immobilized onto aryldiamine modified ZnPS-PVPA with different ratio of phosphonate/phosphate for asymmetric epoxidation were synthesized and characterized by FT-IR, diffusion reflection UV-Vis, MS, N-2 volumetric adsorption, SEM, TEM, XPS, XRD and TG. The supported catalysts displayed superior catalytic activities in the asymmetric epoxidation of alpha-methylstyrene and indene with m-CPBA and NaIO4 as oxidants. Moreover, the heterogeneous catalysts were relatively stable and could be recycled nine times in the asymmetric epoxidation of alpha-methylstyrene. Furthermore, this novel type of catalyst could also be validly used in large-scale reactions with superior catalytic disposition being maintained at the same level, which possessed the potentiality for application in industry. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.