A living free radical polymerization process was adopted to synthesize a narrow polydispersity fullerene-end-capped polystyrene(NPFECPS). The UV-Vis, DSC, GPC demonstrated that fullerene(C-60) was chemically bonded to polystyrene successfully, and C-60 was almost monosubstituted. The NPFECPS can be dissolved in a variety of solvents, such as THF, toluene, trichloromethane, and so on. The good photoconductivity is also found for NPFECPS.