Titanium complexes (1-3) of unsymmetric N2O2 ligands (H2L) were prepared. The reaction of H2L with NaH and then with TiCl4 in THF gave a mononuclear complex LTiCl2 (1). In the presence of 0.5 equiv of water in THF, the hydrolysis of complex 1 produced an oxo-bridged dinuclear complex (mu-O)[ LTiCl](2) (2). The mononuclear Ti complex LTi((OPr)-Pr-i)(2) (3) was prepared by combining H2L with Ti(OiPr)(4) in dry toluene. Complexes 1-3 are able to catalyze the living control ring-opening polymerization (ROP) of lactide to afford polylactide (PLA) with a narrow molecular weight distribution (M-w/M-n= 1.03-1.19). The kinetic studies show a first-order dependency in monomer. The microstructure analysis of the resultant polymer implies that the complexes possess isotactic selectivity and the isotactic-riched polylactide (P-m = 0.68-0.73) can be produced. The polymerization of L-lactide proceeds at a faster rate than the polymerization of rac-lactide, which is consistent with the isoselectivity in the polymerization.