An amphiphilic rod-coil ABC triblock copolymers using rigid oligo(para-phenylencethynylene) (OPE) as the middle rod segment, poly(ethylene oxide)-block-oligo(para-phenyleneethynylene)-block-polystyrene (PEO-b-OPE-b-PS). was designed and successfully synthesized. In the synthetic route, a kind of macroinitiator, PEO-b-OPE-Br was achieved by stepwise coupling of iodo-terminated poly(ethylene oxide) and oligo(para-phenyleneethynylene) with amino end group, capping with 2-bromopropionyl bromide. Subsequently, from this macroinitiator atom transfer radical polymerization (ATRP) of styrene was performed to obtain PEO-b-OPE-b-PS. The resulting copolymers were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). All these novel copolymers were affirmed to have well-defined structures and narrow molecular weight distributions. (c) 2005 Elsevier Ltd. All rights reserved.