A new titanium alkoxide, Ti[OCH2CCl3](4), designed to combine the ring-opening polymerization (ROP) of epsilon-caprolactone and atom transfer radical polymerization (ATRP) of n-butyl acrylate, was synthesized through the ester-exchange reaction of titanium n-propoxide and 2,2,2-trichloroethanol. The mechanism and kinetics of Ti[OCH2CCl3](4) initiated bulk polymerization of e-caprolactone were studied. The results demonstrate that the polymerization proceeds through the coordination-insertion mechanism and all the four alkoxide groups in Ti[OCH2CCl3](4) share a similar activity in the initiation. The determined polymerization activation energy is 70 kJ/moL The polymerization process can be well predicted by the obtained kinetic parameters. Furthermore, PCL synthesized with Ti[OCH2CCl3](4) can be used as the macroinitiator in ATRP of n-butyl acrylate to synthesize poly(epsilon-caprolactone)-block-poly(n-butyl acrylate) (PCL-b-PBA) copolymer. (c) 2009 Elsevier Ltd. All rights reserved.