Abstract: Using sucrose and bio-diesel as raw materials, the condition of sucrose esters (SE) synthesis with solventless method was optimized. The optimum conditions of SE synthesis at 130℃ for 3 h with the mole ratio of bio-diesel to sucrose 1:1-4:1 were obtained by using 2% potassium carbonate as catalyst and 10% potassium stearate as co-solvent under vacuum less than 0.09 MPa. Mixed solvent extraction was used to purify raw product to obtain high-qualified sucrose esters of bio-diesel. The yield can reach 78%.