A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp2TiCl2 and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(c-caprolactone) or poly(L-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp2Ti(III)Cl which is generated in situ via the reaction of Cp2TiCl2 with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups. (C) 2010 Elsevier Ltd. All rights reserved.