The most commercially successful aliphatic polyester today namely polylactide (PLA) has found applications in packaging materials, biomedical devices and a variety of commodity consumer products. Unfortunately, regular PLA shows a moderate glass transition temperature (Tg = 50-60 °C).1 Hence it is a poor alternative to glassy petroleum-based polymers such as polystyrene (Tg = 100 °C). Aliphatic and aromatic alternating polyesters have found to be the suitable alternatives of synthetic petroleum-based polymers as they are biodegradable and biocompatible.2 The alternating polyester can be synthesized by the ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides. The ROCOP of cyclohexene oxide (CHO) with anhydrides to give fully alternating polyesters has grabbed the research interests of researchers globally due to their high glass transition temperature.3 The respective polymers have been extensively used as plastics, fibers and films for engineering, packaging and biomedical materials.4 To date there are numerous reports for the ROCOP of epoxides and cyclic anhydrides using metal complexes containing achiral ligands and the use of chiral metal complexes in this area is unexplored. We synthesized chiral monomeric (S) and (R) isomer of aluminum complexes and investigated their catalytic activity towards ROCOP of CHO and cyclic anhydrides (Phthalic anhydride, succinic anhydride and maleic anhydride) to produce fully alternating polyesters. The polymerizations were carried out under various conditions and from this study we made a correlation of the selectivity, molecular weight (Mn) and polydispersity (Đ) of the synthesized polyesters with changing the catalyst chirality. These Al(III) compounds with an ionic cocatalyst show notable catalytic activity producing alternating polyester with TOF up to 80 h−1, high selectivity (polyester linkages > 80%) and moderate to high Tg. The catalytic activities of the two enantiomers of the Al(III) compounds have been investigated, where the (S)-isomer is found to be more active towards the ROCOP.