The selective synthesis of tri- and dichlorotitanium species containinc chiral tridentate Schiff base ligands, derived from (1 R,2S)-(-)-1-aminoindanol, wets achieved by changing the solvent. Single-crystal X-ray analyses reveal that chlorotitanium complexes are monomeric and octahedral with the meridional occupation of the Schiff base. Although the chlorotitanium complexes lack typical initiating groups such as alkoxides or amides, they are effective catalysts for the controlled ring-opening polymerization Of L-lactide (L-LA) as shown by the linearity of the molecular weight vs [L-LA]/[Ti] ratio plot as well as very narrow polydispersity index values.