A series of aluminium complexes supported by amidinate-based N,O-chelate ligands are synthesized and characterized. While complexes [L(Dipp)AlMe2] () and [L(Ph)AlMe2] () are prepared by treating N-benzoyl-N'-2,6-diisopropylphenylbenzamidine (L(Dipp)H) and N-benzoyl-N'-phenylbenzamidine (L(Ph)H) with a slight excess of 1 equiv. of AlMe3, complexes [(L(Dipp))2AlMe] () and [(L(Ph))3Al] () can be obtained using the ligands and AlMe3 in 2 : 1 and 3 : 1 molar ratios respectively. Complexes have been characterized by (1)H/(13)C NMR spectroscopy and elemental analysis. The molecular structures of complexes , and have also been determined by single crystal X-ray diffraction technique. , and are highly active initiators for the ring opening polymerization (ROP) of ε-caprolactone and produce polycaprolactone with very high molecular weight and narrow molecular weight distribution. These complexes are also active toward the ROP of cyclohexene oxide.