The present invention relates to a method for high selectivity co-production of adipic acid and nitrocyclohexane. According to the present invention, a nitrogen oxide NOx is adopted as an oxidant and a nitrating agent to carry out one step high selectivity conversion of cyclohexane into adipic acid and nitrocyclohexane, and adjustments of a reactant ratio, a reaction temperature, a reaction pressure, a type and an amount of a catalyst or an induction agent, and other conversion conditions are adopted to achieve regulation of a production ratio of the adipic acid and the nitrocyclohexane; and NO produced from the reaction can be recycled and then reacts with oxygen to be converted into NOx so as to be recycled.