A terpyridine-functionalized alkoxyamine unimolecular initiator was used for the nitroxide-mediated controlled living radical polymerization of n-butylacrylate, N,N-dimethylacrylamide, 4-vinylpyridine, 2-vinylpyridine, and isoprene. For the former three monomers, the kinetics were studied. All polymerizations resulted in well-defined polymers having a single terpyridine ligand at the chain end and narrow polydispersity indices. The obtained polymers are valuable building blocks for metallosupramolecular polymers. (c) 2005 Wiley Periodicals, Inc.