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Endohedral fullerenes represent a novel type of nanocarbons, which are characterized by a robust fullerene cage with atoms, ions, or clusters trapped in its hollow. We are endeavoring to synthesize novel endohedral fullerenes with special focus on clusterfullerenes such as Sc3N@C82, TiSc2N@C80, Sc2S@C82, YCN@C82, and aiming to enlarge the family of endohedral fullerenes to understand their formation mechanism and explore their potential applications in e.g. polymer solar cells. Endohedral fullerenes would be isolated by High Performance Liquid Chromatography (HPLC) and characterized by a number of spectroscopic methods (MS, UV-vis-NIR, FTIR, Raman, NMR) as well as X-ray crystallographic and electron microscopic study. Furthermore, novel nanostructures of endohedral fullerenes have been also prepared toward the applications in energy and catalysis etc.