A "click" polymerization of dialkynes that contain an ester linkages and diazides to has been performed to synthesize various polyesters, termed "click polyesters" with a high (M) over bar (n) of 1.0 x 10(4) to 7.0 x 10(4) in an excellent yield. This polymerization accompanied a formation of 1,4-disubstituted triazoles in the polyester main chain by a Cu-I catalyst. The triazole ring formation in the Dolvester main chain leads to improved thermal properties and enhancement of the even-odd effect of methylene chain length of the produced click polyesters. This report is the first report of the application of click chemistry to synthesize a series of polyesters under mild conditions.