The reaction of oxidation of cyclohexane catalyzed by NHPI/SMA-Co multiple active site was studied in this paper. The optimum reaction conditions were as follows: 5mL of cyclohexane, 10mL of acetonitrile, the molar ratio of NHPI/SMA-Co is 10:3, HHPI/SMA-Co composite catalyst dosage is 0.04g, reaction temperature is 120℃, reaction pressure is 1.0MPa. React time is 6h, under these conditions, the conversion of cyclohexane was 19.84%, the selectivity of cyclohexanol was 22.23%, the selectivity of cyclohexanone was 38.65%, and the selectivity of KA was 60.88%. Repeated use experiments showed that the catalyst could be recycled.