Monoalkynyl-functionalized fullerene was precisely synthesized starting with pristine fullerene (C-60) and characterized by multiple techniques. Methyl methacrylate and 6-azido hexyl methacrylate were then randomly copolymerized via reversible addition fragmentation chain transfer polymerization to build polymer backbones with well-controlled molecular weights and copolymer compositions. Finally, these two moieties were covalently assembled into a series of well-defined side chain fullerene polymers (SFPs) via the copper-mediated click reaction which was verified by Fourier transform infrared spectroscopy and H-1 NMR. The fullerene loadings of the resultant polymers were estimated by thermogravimetric analysis and UV-vis spectroscopy, demonstrating consistent and high conversions in most of the samples. The morphology studies of the SFPs were performed both in solution and on solid substrates. Very intriguing self-aggregation behaviors were detected by both gel permeation chromatography and dynamic light scattering analyses. Furthermore, the scanning electron microscopic images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline-like clusters depending on the fullerene contents and polymer chain lengths. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3572-3582