A series of monomeric zinc silylamido complexes bearing [NNNO]-type tetradentate aminophenolate ligands, LZnN(SiMe3)(2) [L = {(2-R-1)ArCH2N[(CH2)(2)R-2]CH2(4-R-4-6-R-3)C6H2O-}, R-1 = NMe2, R-2 = (NPr2)-Pr-i, R-3 = R-4 = Cl (I), R-3 = R-4 = cumyl (3); R-1 = NMe2, R-2 = NEt2, R-3 = R-4 = cumyl (2), R-3 = CPh3, R-4 = Me (4); R-1 = NEt2, R-2 = NEt2, R-3 = CPh3, R-4 = Me (5); R-1 = NMe2, R-2 = (S)-1-butylpyrrolidin-2-yl, R-3 = R-4 = cumyl (6), R-3 = CPh3, R-4 = Me (7)], have been synthesized via reactions of Zn[N(SiMe3)(2)](2) and 1 equiv of the corresponding aminophenols. The monomeric nature and versatile coordination patterns of these complexes in the solid state were further confirmed by X-ray diffraction studies on complexes 2, 3, 5, and 7. In complex 3, the N,N-diisopropylamino group on the pendant side arm does not coordinate to the metal center; only the remaining three donors of the aminophenolate ligand and the silylamido group interact with the zinc center. By contrast, in complexes 2, 5, and 7, the amino group of the aryl moiety does not coordinate to the metal center, while the amino group on the pendant side arm coordinates. At room temperature, the above-mentioned structural features of these complexes are retained in solution, as confirmed by 'H NMR spectroscopy. Complexes 1-7 proved to be efficient initiators for the ring-opening polymerization of rac-lactide (rac-LA) at ambient temperature, and the polymerizations were better controlled in the presence of 2-propanol. The coordination pattern of the aminophenolate ligand exerted a significant influence on the stereoselectivity of the corresponding complex toward the polymerization of rac-LA, leading to the production of heterotactic biased polylactides (PLAs) by complexes 1 and 3 (P-m = 0.40-0.46) and moderately to highly isotactic PLAs by complexes 2 and 4-7 (P-m = 0.70-0.81). Detailed kinetic investigations revealed a first-order dependence on the monomer concentration for all complexes and different orders in the initiator concentration ranging from 1.78 to 1.81. The nature of the solvent as well as the molar ratio of the zinc complex and 2-propanol also displayed certain influence on the order of rac-LA polymerization in the initiator concentration. Factional. orders of 1.80, 1.38, and 1.11 were obtained by using complex 5/(PrOH)-Pr-i (1:1) in toluene and tetrahydrofuran and complex 5/(PrOH)-Pr-i (1:2) in toluene, respectively. On the basis of DOSY and H-1 and C-13 NMR studies of zinc alkoxide model complexes "LZn(OCMe2COOMe)" as well as the fractional orders of 1.78-1.81 in the initiator concentration, activation/insertion processes likely involving more than one monomeric active species were then hypothesized.