C60Cln-m bonded poly(N-vinylcarbazole) (C-60-PVK) has been synthesized by C(60)Cln (the average value of n is 20)/CuCl/Bpy (2,2'-bipyridine) catalyst system and its structure was analyzed by UV-Vis and proton NMR. The polymerization mechanism was proposed proceeding via a atom transfer radical polymerization (ATRP). The block copolymer of poly N-vinylcarbazole-block-polystyrene can also be compounded by adding styrene after N-vinylcarbazole polymerized completely in this polymerization system. The photoconducting properties of C60Cln-m-bonded poly(N-vinylcarbazole) was better than poly(N-vinylcarbazole) initiated by AIBN.