The copolymerization of N-phenyl maleimide and p-chloromethyl styrene via reversible addition-fragmentation chain transfer (RAFT) process with AIBN as initiator and 2-(ethoxycarbonyl)prop-2-yl dithiobenzoate as RAFT agent produced copolymers with alternating structure, controlled molecular weights, and narrow molecular weight distributions. Using poly(N-phenyl maleimide-alt-p-chloromethyl styrene) as the macroinitiator for atom transfer radical polymerization of styrene in the presence of CuCl/2,2 '-bipyridine, well-defined comb-like polymers with one graft chain for every two monomer units of backbone polymer were obtained. (c) 2006 Wiley Periodicals, Inc.