Selective aerobic oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) with high yield under mild and green conditions is still a significant challenge in the current chemical industry. Herein, nitrogen doped graphene loaded non-noble Co (Co-N-rGO) catalysts, prepared by a facile post-impregnation method, exhibited a high catalytic performance and stability in liquid phase cyclohexane oxidation with molecular oxygen. The experiment and characterization results show that N doping in the catalysts promotes Co metal particle dispersion and induces carbon film coating on Co to prevent leaching and agglomeration. Besides, density functional theory (DFT) calculations show that N doping is beneficial to the O-O bonds breaking in cyclohexyl-hydroperoxides (CHHP), thereby promoting the dissociation of CHHP and enhancing the yield to KA oil. In addition, the catalyst can be easily separated without appreciable loss of catalytic activity after recycling for five times, and show potential industrial application value for the catalytic oxidation of cyclohexane to KA oil in the chemical industry.