Buckminsterfullerene C-60 core functionalised core cross-linked star (CCS) polymers have been prepared for the first time, using atom transfer radical polymerisation and the arms-first approach. A simple and efficient method is presented which allows the construction of star polymers consisting of a large number of arms and multiple units Of C-60 per core, far in excess of that obtained previously. The C-60 CCS polymers were characterised by gel permeation chromatography (GPC), UV-vis spectroscopy and cyclic voltammetry (CV). GPC revealed that the C-60 CCS polymers possess weight average molecular weights (M-w) ranging from 172-411 kDa and up to 30 arms per macromolecule. The average number of molecules Of C-60 Per CCS polymer core was found to be dependent on the C-60/PMMA ratio employed and was determined by UV-vis spectroscopy to range up to 6.2. CV revealed that, like pristine C-60, the C-60 CCS Polymers possessed three reversible one electron reductions. However, the reduction potentials were positively shifted, implying that the electron affinity of these macromolecules is higher than pristine C-60. (C) 2008 Elsevier Ltd. All Lights reserved.