Selective oxidation of cyclohexene was carried out using tin deuterporphyrin dimethyl ester as catalyst with dioxygen. The effect of various reaction parameters, such as reaction time, temperature, pressure and the amount of the catalyst on the conversion of cyclohexene and the selectivity of product on the catalytic performances, was investigated in detail as well as online analysis by GC-MS detection. It was demonstrated that under optimal reaction conditions like 100 ℃, 0.8 Mpa, 7 h, 0.5 mg (7.6?0-4 mmol) catalyst and 10 mL (98 mmol) cyclohexene, the conversion of cyclohexene and the total selectivity of the corresponding product(2-cyclohexen-1-one and 2-cyclohexen-1 -ol) were 84% and 94%, respectively. Furthermore, the reaction mechanism of catalytic oxidation reaction was also preliminarily discussed.