Novel catalytic and initiating systems based on CuBr/2,2'-bipyridine (bpy), CuCl/bpy, Cu2O/bpy, and CuO/bpy, in the presence of alkyl, alkylsulfonyl, and arenesulfonyl halides, for the living radical polymerization (LRP) of acrylonitrile (AN) are reported. The optimum combinations of catalyst and initiator are CuCl/bpy and 2-chloropropionitrile (CPN), CuCl/bpy and trichloromethanesulfonyl chloride (TCMSC), Cu2O/bpy and 2-bromopropionitrile (BPN), Cu2O/bpy and 4-methoxybenzenesulfonyl chloride (MBSC), and CuO/bpy and methanesulfonyl chloride (MSC). The first example of a three-arm star polyacrylonitrile (PAN) was synthesized by the LRP of AN using 1,1,1-tris(4-chlorosulfonylphenyl)ethane (3PSC) initiator, in the presence of Cu2O/bpy catalyst.