Controlled polymerization of styrene in toluene was achieved by atom transfer radical polymerization (ATRP) using hyperbranched polyglycidol-supported multidentate amine ligands/(CuBr)-Br-I catalyst systems. These catalyst systems with nanoscopic dimensions were more active than the corresponding low-molecular-weight ligands. The controlled/living nature of the polymerization is supported by linear first order plots (ln[M](o)/[M] versus time) and a linear increase of (M) over bar (n) versus conversion as well as low polydispersity. Similar controlled polymerization of methyl methacrylate was possible in acetonitrile. Up to 97% of total copper used for polymerization could be removed from the polymer by simple precipitation in methanol and filtration.