The reaction of the selective catalytic oxidation of cyclohexanol to cyclohexanone using 30 wt% H2O2 as an oxidant and sodium tungstate as a catalyst was studied. The influencing factors in the reactions such as ligand types, the ratio of sodium tungstate and the ligand, reaction time, reaction temperature, the amount of catalyst and oxidant were investigated. The experimental results showed that the addition phosphotungstic acid into the system could obviously increase the yield of cyclohexanone. Under the beneficial conditions (i.e. cyclohexanol of 10 mL, sodium tungstate of 1.1 mmol, phosphotungstic acid of 0.11 mmol, 30 wt% hydrogen peroxide of 35 mL, the reaction temperature at 80 °C, reaction time for 5 h), the yield of cyclohexanone could reach 80.99%.