C-60 bonded poly(N-vinylcarbazole) has been synthesized by C(60)Cln (the average value of n is 20)/CuCl/2,2'-bipyridine (Bpy) catalyst system and its structure was analyzed by UV-Vis and proton NMR. The polymerization mechanism was proposed proceeding via an atom transfer radical polymerization (ATRP). The photoconducting properties of C-60 bonded poly(N-vinylcarbazole) was better than poly(N-vinylcarbazole) initiated by AIBN.