Herein, a series of enantiocomplementary polyesters with either (S)- or (R)-configurations were successfully prepared by applying a dual-enzyme biocatalytic system. In the step of Baeyer-Villiger oxidation, cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 (CHMOAcineto) was engineered rationally to tailor the enantiopreference of mutants, providing (S)- and (R)-lactones, respectively, with high optical purities (up to 99% ee) as polymeric precursors. By subsequent enzymatic ring-opening polymerization of the enantiopure monomers, enantiocomplementary polyesters with high molecular weight (up to 21.8 kDa Mn) were synthesized by lipase CALB/MML. Our research offers an environmentally friendly synthesis route for the production of optically pure lactones and chiral polyesters, which are of particular significance for their application in organic syntheis or biomedical materials.