<p>Chemical modification of polymers represents a pivotal method for achieving functionalized polymer materials. However, due to the lack of post-functional handle, the chemical modification of polyester materials remains a significant challenge. Ring-opening copolymerization of cyclic anhydride and epoxides is a powerful approach to synthesize polyesters. In this work, we for the first time demonstrate the functionalizability of polyesters synthesized with brominated anhydride monomers. The post-functionalization is amenable to a wide variety of reactive groups and reactions with high yields. With multiple well-established functionalization pathways of brominated polyester materials and optimized the conditions for the modification reactions, a series of functionalized polyester materials can be obtained with high yields, providing new insights for the research about functionalization of polymers.</p>