The present invention relates to a catalyst for high-selective catalytic oxidation synthesis of cyclohexanol/cyclohexanone from cyclohexane. The catalyst uses a transition metal Schiff base complex as an active component, uses silica gel as a carrier, silica gel: chromium Schiff base complex=1 g: 0.05-0.5 mmol. Compared with an existing catalyst, the catalyst has the following advantages: (1) the preparation method of the catalyst is simple and easy to operate; (2) in the cyclohexanol synthesis reaction, the conversion rate of cyclohexane is high, and the selectivity of the product cyclohexanol is good; (3) the repeated use performance of the catalyst is good; (4) the cost is low, and the reaction conditions are mild and green.