The tetramer titanium alkoxide (MeC(CH2-mu(3)-O)(2))(2)Ti-4(O-i-Pr)(10), (1) catalyzes the ring-opening polymerization (ROP) of lactide (LA) in toluene solution at various polymerization temperatures, and its bulk ROP at 130degreesC. Compound 1 facilitated reasonably controlled polymerization characteristics via a coordination/insertion mechanism in solution, whereas the bull polymerization products displayed broad molecular weight distributions. The stereochemical microstructure of PLA was determined from homonuclear decoupled H-1 NMR spectroscopic studies.