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Mono(ketiminate) aluminum dimethyl complexes 1a – 5a and bis(ketiminate) aluminum methyl complex 2b were synthesized via the reactions of AlMe 3 with various N -aryl substituted ketimine compounds in a 1:1 or 1:2 molar ratio, respectively. The reaction of Al(O i Pr) 3 with the ketimine compound L 2 H resulted in a bis(ketiminate) aluminum isopropoxide complex 2c . All the complexes were characterized by 1 H and 13 C{ 1 H} NMR spectroscopy, either EA or HRMS analysis. X-ray diffraction measurement of complexes 2a and 3a confirmed that in the solid state both 2a and 3a exist as a tetrahedron structure with the aluminum atom center surrounded by the oxygen and nitrogen donors of the bis-chelating ketiminate ligand as well as two methyl groups. Besides, a triligated aluminum complex 3 (Al(L 3 ) 3 ) with a six-coordinated metal core and a dinuclear aluminum isopropoxide complex 6d [(L 6 ) 2 Al(μ-O i Pr) 2 Al(O i Pr) 2 ] with C 2 -symmetry were isolated and characterized by X-ray diffraction studies. All aluminum methyl complexes behaved as active initiators in the ring-opening polymerization (ROP) of rac- lactide ( rac -LA), affording isotactic-enriched polylactides (PLAs) with high molecular weights and broad molecular weight distributions at 70 °C. The steric and electronic characters of the ancillary ligands show significant effects both on the activity and the stereoselectivity. The introduction of an electron-withdrawing group on the para -position of N -aryl ring of the ligand resulted in an increase of the catalytic activity. However, the electronic character of ancillary ligands showed a neglectable effect on the ROP of ε -CL initiated by these aluminum complexes. For both monomers, bis(ketiminate) aluminum complex 2b was found to be more active than the corresponding mono(ketiminate) complex 2a of the same ligand. Aluminum isopropoxide complex 2c exerted better control for the polymerizations of both monomers, providing polymers with narrower molecular weight distributions and smaller molecular weights which are comparable to the theoretical values [ABSTRACT FROM AUTHOR]