A series of typical methyl regulators were used to finely modify the Cr(salen) complex immobilized on MCM-41. Such immobilized complexes were effective catalysts for solvent-free selective oxidation of benzyl alcohol (BzOH) with 30% hydrogen peroxide (H2O2), and they all exhibited much higher catalytic performance than their homogeneous analogue. Simultaneously, the introduction of methyl regulators was found to significantly improve the catalytic performance of immobilized complexes by modifying their surface properties. The optimal BzOH conversion reached 65.0% with 100% selectivity to benzaldehyde (BzH).