2-Hydroxy-1,4-cineole(Ⅱ) is the intermediate of a botanical cineole derivative herbicide Cinmethylin. It can be obtained from terpinen-4-ol(Ⅰ) via an one-step synthetic method by using peroxoheteropolyoxomolybdotungstate (Cat-PMo2W2O24) as redox–acidic bifunctional catalyst in presence of mass fraction 30 % H2O2 aqueous solution. There were obvious effect of various reaction parameters such as solvent type, catalyst dosage, and the amount of hydrogen peroxide on the phase state, acidity or acid amount of reaction system, resulting in the changes of the conversion rate ofⅠand the yield of Ⅱ. Under the optimum conditions(Ⅰ,12 mmol; chloroform as solvent,5 ml; catalyst dosage,4.20 %(mass fraction, based on the substrate);temperature，25℃; the molar ratio of H2O2 toⅠ, 0.91; reaction time, 30 min.), 96.2% conversion of Ⅰ with 70.1% yield towards Ⅱ was achieved.