A family of aluminum complexes containing anilido-oxazolinate ligands are described. Reactions of five anilido-oxazolinate ligand precursors, HNPh(TriMe)Oxa, HNPh(DiiPr)Oxa, HNPh(OMe)Oxa, HNPh(SMe)Oxa, or HNPhOxa, with 1 molar equiv. of AlMe(3) in toluene give the aluminum dimethyl complexes (NArOxa)AlMe(2) [Ar = 2,4,6-trimethylphenyl, (NPh(DiiPr)Oxa)AlMe(2) (1); Ar = 2,6-diisopropylphenyl, (NPh(DiiPr)Oxa)AlMe(2) (2); Ar = 2-methoxyphenyl, (NPh(OMe)Oxa)AlMe(2) (3); Ar = 2-methylthiophenyl, (NPh(SMe)Oxa)AlMe(2) (4); Ar = phenyl, (NPhOxa)AlMe(2) (5), respectively]. The molecular structures are reported for compounds 1-4. Their catalytic activities toward the ring-opening polymerization reactions of L-lactide or epsilon-caprolactone in the presence of BnOH are also under investigation. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009