Two series of titanium complexes, including salicylbenzoxazole titanium complexes (1-4) and salicylbenzothiazole titanium complexes (5-8), were successfully synthesized and characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction crystallography (for 2 and 5). The 1H NMR spectra of complexes 7 and 8 reveal fluxional behavior in solution at room temperature, and the activation parameters were determined by lineshape analysis of variable-temperature (VT) NMR spectra in toluene-d8: for 7, ΔH⧧ = 73.0 ± 1.8 kJ mol-1, ΔS⧧ = 22.1 ± 5.5 J mol-1 K-1; for 8, ΔH⧧ = 73.7 ± 1.2 kJ mol-1, ΔS⧧ = 20.3 ± 3.8 J mol-1 K-1. The positive values of ΔS⧧ suggested that the isomerization occurred via a dissociative mechanism. All complexes were active initiators for the ring-opening polymerization of ε-caprolactone (ε-CL) and three substituted ε-CLs: γ-methyl-ε-caprolactone (γMeCL), γ-ethyl-ε-caprolactone (γEtCL), and γ-phenyl-ε-caprolactone (γPhCL). Of all complexes, complex 5 was found to be the most active initiator in this study. The copolymerizations between ε-CL and three substituted ε-CLs produced completely random copolymers. The polymerization was proposed to proceed via a dissociative coordination-insertion mechanism. The catalytic activity of the salicylbenzoxazole titanium complex was lower than that of its closely related salicylbenzothiazole titanium congener. Additionally, DFT calculations unveiled that the ligand decoordination step and the less steric congestion at the titanium center in the salicylbenzothiazole titanium complexes were the key factors in enhancing the catalytic rate.