Esters of Citric acid and palmityl alcohol were synthesized by esterification reaction under catalysis of cation exchange resin and P-toluene sulfonic acid respectively. The effects of amount of catalyst, ratio of raw materials, reaction time and temperature on the synthesis reaction were investigated . The experimental results showed that optimum of process conditions were 1:1~1:1.5 molar ratio of citric acid and palmityl alcohol, reaction temperature of 130~140°C, reaction time of 2 h. Conversion of palmityl alcohol were all more than 90% under 0.3% dosage using p-toluene sulfonic acid as the catalyst, or 0.5% dosage using 721 cation exchange resin with sulfonic acid type as catalyst. The synthesized product had good surface activity.