The chloroaluminate ionic liquid,composed of AlCl3 and 1-butyl-3-methylimidazolium chloride(Cl),is used as the solvent and catalyst to synthesize α-hydroxy esters from alkene and glyoxylate via the glyoxylateene reaction.Under the reaction conditions of 15 ℃,4 h,and AlCl3/Cl molar ratio of 2,the ethyl α-hydroxy-4-phenyl-4-pentenoate with high yield(95.2%) is obtained in the reaction of α-methyl styrene and ethyl glyoxylate.Other α-hydroxy esters can also be obtained in high yields through the glyoxylate-ene reaction.Moreover,the chloroaluminate ionic liquid can be reused several times.