A series of lithium and sodium iminophenoxide complexes have been successfully synthesized and characterized by X-ray crystallography and investigated as catalysts for the ring opening polymerization of L-lactide. The nature and steric bulk of the ligands coordinated to the central metal ions greatly influence the catalytic properties. Complexes with bidenate ligands exhibit higher catalytic activity than tridentate counterparts because the third coordination atom contends with L-lactide, which decreases activity. Oxygen is the third atom in the tridentate ligand, providing stronger chelation ability with Li and Na than nitrogen or sulfur and occupies the space with which L-lactide is coordinated.