Reversible addition-fragmentation chain transfer (RAFT) polymerization has emerged as one of the important living radical polymerization techniques. Herein, we report the polymerization of di(ethylene glycol) 2-ethylhexyl ether acrylate (DEHEA), a commercially-available monomer consisting of an amphiphilic side chain, via RAFT by using bis(2-propionic acid) trithiocarbonate as the chain transfer agent (CTA) and AIBN as the radical initiator, at 70 degrees C. The kinetics of DEHEA polymerization was also evaluated. Synthesis of well-defined ABA triblock copolymers consisting of poly(tert-butyl acrylate) (PtBA) or poly(octadecyl acrylate) (PODA) middle blocks were prepared from a PDEHEA macroCTA. By starting from a PtBA macroCTA, a BAB triblock copolymer with PDEHEA as the middle block was also readily prepared. These amphiphilic block copolymers with PDEHEA segments bearing unique amphiphilic side chains could potentially be used as the precursor components for construction of self-assembled nanostructures. (c) 2007 Wiley Periodicals, Inc.