Atom transfer radical polymerization (ATRP) was performed to prepare azide end-functional polystyrene (PSt-N-3) with predesigned molecular weight and narrow polydispersity. Then C-60 end-capped polystyrene was synthesized by reacting C-60 with PSt-N-3. The UV-VIS, DSC, GPC characterizations indicated that C-60 was chemically bonded to the end of polystyrene chain, and the brown powder products, which can be dissolved in THF, CHCl3, DMF, and so forth, were monoadditional and diadditional according to C-60.