Abstract: Four cobalt–deuteroporphyrins were synthesized and used as catalysts for cyclohexane oxidation with air in the absence of additives and solvents. The four kinds of cobalt–deuteroporphyrins show good catalytic performance when temperature was 150 ℃, Catalyst: substrate ≈ 1:4.63 × 105 (mol / mol) and pressure was 0.80 Mpa. Substrate which used four kinds of cobalt–deuteroporphyrins as catalysts, its conversion rate within 4 h had reached more than 14% and the target product alcohol and ketone were formed over 82% selectivity. The catalytic activity of cobalt-3,8-dinitro deuteroporphyrin dimethyl ester was superior to another three kinds of deuteroporphyrins. The alcohol and ketone were formed to 82.30% selectivity at a cyclohexane conversion of 19.34% under the optimum conditions, and turnover number reached to 8.86×104.