Hyperbranched polymers were produced using glycidyl methacrylate (GMA)/CP2TiCl2/Zn as self-condensing vinyl polymerization (SCVP) system. The polymerization is firstly initiated by the epoxide radical ring opening catalyzed by Cp2Ti(III)Cl generated in situ via the reaction of Cp2TiCl2 with Zn. By optimizing the molar ratio of the SCVP inimer (GMA) to the mediator (Cp2Ti(III)Cl), the active propagation chains are reversibly transformed to the dormant species and the cross-linking does not occur until a higher level of monomer conversion (ca. 80%). We detail this facile one-step polymerization technique to prepare highly branched polymers with a multiplicity of particular end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups, which differs from most previously reported SCVP systems. (C) 2010 Elsevier Ltd. All rights reserved.