Keggin-type rare earth ceriummolybdovanadophosphoric of four yuan heteropoly acid salt (CeHPMo11VO40?nH2O)has been synthesized and characterized by FT-IR, X-ray diffraction. CeHPMo11VO40?nH2O showed highest catalytic activity in the yield of cyclohexanol and cyclohexane when cyclohexane as raw materials, H2O2 as oxidant, the optimum reaction conditions are investigated that (amount of catalyst, reaction temperature, reaction time, H2O2 dosage) 0.1mol cyclohexane as a reference, the amount of CeHPMo11VO40?nH2O is 0.2mmol , added 30% hydrogen peroxide 0.2mol ,the reaction temperature is 75 ℃, though reacting 9h, the conversion of cyclohexane was 41.29%, the total yield of cyclohexanol and cyclohexane up to 27.49%.