Metal-catalyzed living radical polymerization of methyl methacrylate initiated with N-chloro amides (N-chloro N-ethyl propionamide, N-chloro benzanilide, N-chloro methylbenzamide, and N-chloro acetanilide), lactams (N-chloro caprolactam and N-chloro 2-pyrrolidinone), carbamates or urethanes (N-chloro ethylcarbamate or N-chlorourethane), imides (N-chloro phtalimide, N-chloro succinimide, trichloroisocyanuric acid, and N-chloro saccharin) and catalyzed with the self-regulated catalytic system Cu2S/2,2'-bipyridine is reported. The initiation efficiency of these initiators is determined by their structure. Regardless of the initiator efficiency, in all cases, poly (methyl methacrylate) with narrow molecular weight distribution and functionalized chain-ends was obtained. These new classes of initiators open new strategies for the functionalization of polymer chain-ends and for the synthesis of complex architectures by graft copolymerization initiated from N-chloro proteins, aliphatic, aromatic and semiaromatic polyamides, and polyurethanes. (c) 2005 Wiley Periodicals, Inc.