Titanium alkoxides are widely used in the ring-opening polymerization of epsilon-caprolactone. In this study, functional poly(epsilon-caprolactone) was synthesized with a new titanium initiator by a two-step procedure: First, the titanium initiator, with an unsaturated group, was prepared by a classical organic reaction between 2-hydroxyethylmethacrylate or 2-allyloxyethanol with titanium tetrapropoxide; then, we initiated the polymerization of the epsilon-caprolactone monomer in a glass reactor or twin-screw extruder. By means of NMR spectroscopy, the structures of the initiators and polymers were determined. When 2-hydroxyethytmethacrylate was used, there was a side reaction (transesterification) during the preparation of the initiator, and so it was impossible to obtain the expected product. With 2-allyloxyethanol, the designed titanium initiator was synthesized with high purity, and the allyl moiety remained intact after the polymerization of F-caprolactone. (C) 2008 Wiley Periodicals, Inc.