Glycerolysis of Chinese vegetable tallow (CVT) fraction was investigated using a 1,3-specific lipase from Rhizopus arrhizus as catalyst. Based upon a binary gradient HPLC with an evaporative light-scattering detector (ELSD), the contents of free fatty acids (FFA), monoglycerides (MG), diglycerides(DG) and triglycerides (TG) with their positional isomers during the glycerolysis were determined. The effects of water content and the ratio of glycerol to oil on the product distribution of glycerolysis were studied. Under the optimum reactant conditions: 250 units lipase per gram oil at 37 degrees C with 1:2 molar ratio of oil to glycerol in a solvent-free system, after 24 h reaction, the product consisted of 7.2% TG, 25.6% MG, 56.1% DG and 4.9% FFA (all by mass). Furthermore, the mechanism of glycerolysis was discussed in detail.