Abstract: The effects of operation parameters on separation of fatty acid methyl ester(FAME) from rapeseed oil deodorizer distillate(RODD) by molecular distillation were investigated for further utilization of RODD. The results indicated that the recovery of FAME was 41 g/(100 mL) when pressure was 5.2 Pa, evaporating temperature was 120℃, feed temperature was 70℃, wiper rolling speed was 150 r/min, feed rate was 120 mL/h. The biodiesel was analyzed by GC-TOFMS. Six fatty acid methyl ester components were determined by normalization method of area. The main components with high relative content include 33.61% palmitic methyl ester, 18.25% linoleic methyl ester, 16.14% oleic methyl ester, 8.81% stearic methyl ester, 7.39% erucic methyl ester, 3.78% gondoic methyl ester. And the total fatty acid ester reaches 89%.