The novel C 60 -styrene copolymers with different C 60 contents were prepared in sodium naphthalene-initiated anionic polymerization reactions. Like the pure polystyrene, these copolymers exhibited the high solvency in many common organic solvents, even for the copolymer with high C 60 content. In the polymerization process of C 60 with styrene an important side reaction, i.e., reaction of C 60 with sodium naphthalene, would occur simultaneously, whereas crosslinking reaction may be negligible. C-NMR results provided an evidence that C 60 was incorporated covalently into the polystyrene backbone. In contrast to pure polystyrene, the TGA spectrum of copolymer containing ฯณ 13% of C 60 shows two plateaus. The polystyrene chain segment in copolymer decomposed first at 300 -400ยฐC. Then the fullerene units reptured from the corresponding polystyrene fragments attached directly to the C 60 cores at 500 -638ยฐC. XRD evidence indicates that the degree of order of polymers increases with the fullerene content increased in terms of crystallography. Incorporation of C 60 into polystyrene results in the formation of new crystal gratings or crystallization phases. In addition, it was also found that [60]fullerene and its polyanion salts [C 60 nฯช (M ฯฉ ) n , M ฯญ Li, Na] cannot be used to initiate the anionic polymerization of some monomers such as acrylonitrile and styrene, etc.