A homotelechelic macroligand bearing two 2,2:6,2-terpyridin-4-yl units, as chain ends, is used as building block for the preparation of a linear metallo-supramolecular chain-extended polymer. The macroligand has been prepared by nitroxide-mediated polymerization (NMP) of styrene using a bis-terpyridine-functionalized NMP initiator. The controlled character of the NMP process has been confirmed by detailed characterization of the polymer by size-exclusion chromatography, nuclear magnetic resonance spectroscopy as well as mass spectrometry. Subsequently, the self-assembly with FeII ions into the chain-extended metallopolymer and the disassembly thereof, in the presence of a strong competitive ligand, has been studied by UVvis absorption spectroscopy and diffusion-ordered NMR spectroscopy. The reversibility of the formation of the metallo-supramolecular material, when addressed by external stimuli, could be proven. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2006-2015