Purely siliceous MCM-41 has been prepared under both mild and acidic condition by a solvent evaporation method using C16TMABr and C22TMACI surfactant as templates. A hydrothermal synthesis was also carried out by utilizing a method of adjusting the gel pH to 10. The mesoporous samples synthesized in ethanol solvent by using this evaporation method showed a fully disordered pore system, but those obtained in the hydrothermal synthesis had highly ordered pores. The chiral salen Mn(III) complexes were immobilized on the siliceous MCM-41 by a new grafting method using 3-aminopropyltrimethylsilane and diformylphenols. These ligands on MCM-41 were stable during the reactions. High enantioselectivities were displayed in the epoxidation of styrene by using these heterogenized salen complexes.