A series of tridentate Schiff base dioxomolybdenum(VI) complexes have been immobilized onto modified synergistic organic-inorganic hybrid support chloromethyl-ZPS-PVPA [zirconium poly (styrene-phenylvinylphosphonate)-phosphate] to prepare a new type of heterogeneous catalyst. The as-synthesized catalysts exhibited good to excellent catalytic efficiency in epoxidation of unfunctionalized olefins, using tert-butyl hydroperoxide (TBHP) as oxidant. Surprisingly, up to 99% ee values were obtained when alpha-methylstyrene was chosen as substrate in this oxidant system with these heterogeneous catalysts. Furthermore, the immobilized catalyst showed a stable catalytic activity in manifold reuses. (C) 2010 Elsevier B.V. All rights reserved.