The liquid-liquid-phase equilibrium of a five-component system of methanol-water-H2O2-trimethylbenzene-trioctyl phosphate was studied, and the data were correlated with UNIQUAC and NRTL models, respectively, and used for the simulation of the extraction of H2O2 with an aqueous methanol solution in the H2O2 production process based on anthraquinone hydrogenationoxidation cycles. The results showed that, with an aqueous methanol solution for the extraction of H2O2, after a few cycles the concentration of methanol in an anthraquinone working solution becomes constant and would not influence the H2O2 production process. All of the impurities in the H2O2 solution obtained with an aqueous methanol solution as the extractant from the H2O2 generation process as well as the stabilizers and corrosion inhibitors that should be added in the H2O2 solution did not appreciably affect the direct ammoximation of cyclohexanone with NH3 and H2O2 catalyzed by TS-1. The results indicated that the processes of cyclohexanone oxime production through the direct ammoximation of cyclohexanone and H2O2 generation through the anthraquinone hydrogenation- oxidation cycles could be integrated.