In this paper, we use mono- and bimetallic complexes based on Earth-abundant, cheap and benign zinc for the synthesis of sustainable aliphatic and semi-aromatic polyesters. Tridentate and hexadentate aldimine-thioetherphenolate ligands were used to obtain the desired zinc complexes by the reaction of proligands with opportune equivalents of zinc bis[bis(trimethylsilyl)amide]. The obtained bimetallic complexes 1 and 2 and the monometallic complex 3 were used as catalysts in the Ring-Opening Polymerization (ROP) of landmark cyclic esters, such as ε-caprolactone and lactide, and in the Ring-Opening COPolymerization (ROCOP) of cyclohexene oxide and phthalic anhydride under different reaction conditions. All catalysts were active in these two classes of reactions, showing good control of the polymerization processes. Interestingly, the bimetallic complexes have higher activity compared to their monometallic counterparts, highlighting the cooperation between the two zinc centers.