The synthesis and structural characterization of bimetallic and trimetallic zinc complexes of amino-bis(phenolate) ligands are described. Bimetallic complexes (ZnEt)₂[L1] (1a), its THF adduct (ZnEt)₂[L1]·THF (1a·THF), and (ZnEt)₂[L2] (1b) (where [L1] = n-propylamine-N,N-bis(2-methylene-4,6-di-t-butylphenolate) and [L2] = n-propylamine-N,N-bis(2-methylene-6-t-butyl-4-methylphenolate) were prepared via reaction of the proligands H₂[L1] and H₂[L2] with ZnEt₂. The addition of isopropanol to complex 1a to replace the ethyl groups with more nucleophilic alkoxyl groups afforded trimetallic zinc complex Zn₃(i-PrO)₂[L1]₂ (3). Their structures were confirmed by X-ray crystallography. Their catalytic activity towards ring-opening polymerization (ROP) of rac-lactide with or without exogenous alcohol as a co-initiator was studied. These complexes exhibit moderate to good activity for ROP of rac-lactide both in the melt phase and solution. The influence of catalyst and co-initiator loadings were studied and thermodynamic activation parameters were determined. Characterization of the polymers by Gel Permeation Chromatography (GPC) and Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrometry showed controlled and living polymerizations for rac-lactide in the presence of alcohol.