Abstract: Eight kinds of α,β-dehydroamino acid esters were synthesized via triethylamine-catalyzed ring-opening methanolysis of azlactones with 62.5%~94.1% yields, which was synthesized from aromatic aldehydes and acetylglycine (or hippuric acid).The structure of the target compounds were characterized by NMR. The effects of the temperature,catalyst and different substituents on the yield of compound 3 were studied. The optimum reaction conditions for the synthesis of compound 3 were obtained in 100℃ and 100%(mol/mol) anhydrous sodium acetate. The electron withdrawing group was more conducive to the reaction. Triethylamine was the best catalyst of compound 4 at room temperature.