The synthesis of cinnamate catalyzed by phosphotungstic acid supported on strong acid cationic resin D001 was studied with cinnamic acid and n-butyl alcohol as beginning materials.The factors effected on the reaction yields, such as the reactants ratios, reaction time, temperature, the amount of catalyst and the reusability of catalyst, were investigated. The result showed that the optimized conditions were as follows: the reaction temperature was 100° C, the reaction time was 3 hours, the ratio of acid and alcohol was 1:3, and the catalyst dosage was 15% (based on total mass of cinnamic acid). Under the optimum conditions, the percentage of esterifation achieves 92.4% and the yield was above 83% after the catalyst was used for 4 times without any treatment. The synthesis of several other cinnamates were also studied in the optimum conditions, and the percentages of esterifation were all over 85%.It was showed that the catalyst of phosphotungstic acid supported on resin D001 has a good catalytic effect.