Synthesis of a novel amphiphilic polymer brush with a sequence of alternating poly(F-caprolactone) (PCL) and poly(ethylene oxide) (PEO) side chains through grafting-through approach is reported. This strategy consists of two steps: first, a PCL macromonomer carrying maleimide functional group (MI-PCL) and a PEO macromonomer with vinylbenzyl group (St-PEO) were prepared; then a conventional radical copolymerization of the MI-PCL and the St-PEO macromonomers was carried out to obtain the proto-type polymer brush. The reactivity ratios of two macromonomers were studied and the alternating sequence structure was proved. (c) 2007 Elsevier Ltd. All rights reserved.