Chemical transformation of spent polyesters into value-added chemicals is substantial for sustainable development but still challenging. Here, we report a simple, metal-free, and efficient aminolysis strategy to upcycle polylactic acid by anilines over lactate-based ionic liquids (e.g., tetrabutylammonium lactate), accessing a series of N-aryl lactamides under mild conditions. This strategy is also effective for degradation of poly(bisphenol A carbonate), affording bisphenol A and corresponding diphenylurea derivatives. It is found that, with the assistance of water, lactate anion as hydrogen-bond donor can efficiently activate carbonyl C atom of polyesters via hydrogen bonding with carbonyl O atom; meanwhile, as hydrogen-bond acceptor, it can enhance nucleophilicity of the N atom of anilines via hydrogen bonding with amino H atom. The nucleophilic attack of N atom of anilines on carbonyl C atom of polyesters results in cleavage of C─O bond of polymers and formation of the target products.