High molecular weight poly(L-lactide)s (PLLAs) and poly(D-lactide)s (PDLAs) were synthesized in toluene at 70 degrees C by ring-opening polymerization of optically pure L-lactide and D-lactide, using tin(II) 2-ethylhexanoate (SnOct(2)) and 2-(2-methoxyethoxy)ethanol as initiator and coinitiator, respectively. Under these conditions, polarimetry as well as C-13 NMR spectroscopy indicated that the synthesized poly(lactide)s (PLAs) are more than 99% isotactic. The molecular weight was successfully controlled by. adjusting the monomer-to-initiator molar ratio. Gel permeation chromatography and MALDI-TOF mass spectrometry analyses showed that the poly-dispersity index of the PLAs is below 1.1. Moreover, MALDI-TOF spectra showed two different chain distributions, one characterized by an even number of lactic acid repeat units and the other by an odd number of lactic acid repeat units. The second distribution, indicative of the presence of intermolecular transesterification reactions, appears at the very beginning of the polymerization and its intensity increases with the polymerization time. Finally, a reversible reaction kinetic model was used to determine the monomer equilibrium concentration ([M](eq) = 1.4 +/- 0.5%) and the propagation rate constant (k(p) = 14.4 +/- 0.5 L mol(-1) h(-1)) of the polymerization. (c) 2006 Wiley Periodicals, Inc.