Click Cu(I)-catalyzed polymerizations of diynes that contained ester linkages and diazides were performed to produce polyesters (click polyesters) of large molecular weights [(similar to 1.0-7.0) x 10(4)], that contained main-chain 1,4-disubstitued triazoles in excellent yields. Incorporation of triazole improved the thermal properties and magnified the even-odd effect of the methylene chain length. We also found that, by changing the positions of the triazole rings, the thermal properties of the polyesters could be controlled. The use of in situ azidation was a safe reaction, as explosive diazides are not used. In addition, the microwave heating was found to accelerate the polymerization rates. This is the first study that has applied click chemistry for the synthesis of a series of polyesters. (c) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 42074218, 2010