A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H2O2 with high selectivity was studied. In this system, heteropolymolybdate [C7H7N(CH3)3]3 {PO4[MoO(O2)2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.