Chem. Sci., 2026, Advance Article DOI: 10.1039/D6SC04630D, Edge Article Ji Xian, Guojie Li, Linyun Wu, Hongjun Fu, Chunmei Wang, Shaoyu Lü, Xiaobo Pan, Jincai Wu Highly alternating copolymerization of L-lactide and ε-caprolactone is achieved via an enantiomorphic site and chain-end synergistic control strategy. This strategy yields sequence-controlled polyesters with exceptional regularity (Palt > 0.90).