In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid ( PSA). Then PSA was applied to synthesis of epsilon-caprolactone (epsilon-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing epsilon-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and (HNMR)-H-1 (H-1 nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of epsilon-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of epsilon-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.