Rapeseed oil deodorizer distillate was an important source of natural vitamin E. Molecular distillation and enzymatic reaction were applied for concentration of vitamin E. The model of content of fatty acid methyl ester produced by enzymatic reaction was presented by response surface methodology (RSM) on the basis of molecular distillation and single factor experiments . The results indicated that when material 20g, reaction temperature 37℃,the amount of water 11.7ml and Candida rugosa lipase 30.78 U for hydrolysis time 16h followed by amount of methanol added 1.32ml with lipase 15 U per time of three times, and total reaction time 40h, the content of vitamin E was 25% after twice molecular distillation.