A zinc complex with the Schiff base [(CH3)(2)NCH2CH2N=CHC6H3(OH)(OMe)], LH, derived from 2-dimethylaminoethylamine and o-vanillin [Zn2L2(OBn)(2)], has been synthesized and its structure has been established by X-ray crystallography and NMR spectroscopy. This zinc complex efficiently initiated the ring-opening polymerization (ROP) of L-lactide (L-LA), and the polymerization runs were well controlled, giving polylactide end-capped with benzyl ester and hydroxyl groups. The structure of the ancillary ligands showed some influence on the catalytic activity, the introduction of electron-rich methoxy at ortho-phenoxy substituent resulted in a decrease of the polymerization rate. In addition, we also have found that the overall rate expression is d[lactide]/dt = k(p)[lactide](1) [Zn2L2(OBn)(2)](1) in the kinetic study with the ROP of L-LA. (C) 2011 Elsevier B.V. All rights reserved.