Tert-butyl hydroperoxide and di-tert-butyl peroxide were synthesized by oxidation of tert-butyl alcohol with hydrogen peroxide using 12-phosphotungstic acid as catalyst. The effects of temperature，reaction time，mass of catalyst，dosage ratio of raw materials on the reaction were investigated in the ways of single factor and orthogonal design methods. Under the conditions that the molar ratio of tert-butyl alcohol to hydrogen peroxide is 0.7：1，the molar ratio of tert-butyl alcohol to phosphotungstic acid is 299:1，the reaction temperature at 83℃ and the reaction time with 3 h，the conversion of tert-butyl alcohol could reach to more than 95%，the yield and selectivity of tert-butyl hydroperoxide are 75.9% and 79.6%，respectively.