A novel calcium complex, [(DAIP)(2)Ca](2) (where DAIP-H = 2-[(2-dimethylamino)methyl]phenol, is prepared in a one flask reaction by condensation of Ca(OMe)(2) with DAIP-H in toluene/THF Experimental results show that in the presence of various alcohols, [(DAIP)(2)Ca](2) efficiently initiates the ring-opening polymerization Of L-lactide in a controlled fashion, yielding polymers with expectative molecular weight and low polydispersity indexes. Furthermore, kinetic studies show a first-order dependency on both [LA] and [BnOH]. (c) 2007 Elsevier Ltd. All rights reserved.