The oxidations products of styrene have a wild range of application, which are important synthesis intermediate. However, their traditional preparation have multi-step reactions, low utilization of raw material, various by-products and serious corrosion to equipment , which are contrary to green chemistry and atom economical reaction. Meanwhile with the development of extraction 、separation 、purification and immobilization , enzyme can be large-scale used in chemical industry. Enzyme catalysis have some virtues such as high efficiency in catalytic reaction, high selectivity, mild reaction conditions and friendly to environment .We synthesize 1-Phenyl-1,2-ethanediol by direct oxidation process with styrene and H2O2 as raw material, Novozym435 as catalyst in solvent-free system. The optimum reaction conditions are as follows: the concentration of H2O2 is 20%, the molar ratio of styrene/H2O2 is 0.9,the reaction temperature is 50 ℃and reaction time is 24 h, the mass ratio of Novozym435 is 0.5%.The result shows that the maximum conversion of styrene could reach 93.7%,the selectivity of 1-Phenyl-1,2-ethanediol could reach 87.76%.After purification and recrystallization , we got white needle crystal whose melting point is 65-67 ℃. This paper use different quaternary ammonium peroxotungsto phosphate salt as catalyst which are Q+3{PO4[W(O)O4]3[W(O)O4]}3-（Q+：Bu4N+、(C8H17)3CH3N+ and π-C5H5N+C16H33）.Meanwhile, we investigate the oxidation of styrene with 1,2-dichloroethane as solvent , H2O2 as oxidation. The result shows that [(C8H17)3CH3N+]3{PO4[W(O)O4]3[W(O)O4]}3- has proper catalytic effect. The conversion of styrene could reach 40.2% , meantime, the selectivity of styrene oxidation arrive at 29.2% in the case that medium pH is 3.0, the molar ratio of catalyst, styrene and H2O2 is 1:100:120 in 55 ℃.