Single electron transfer-living radical polymerization (SET-LRP) of two amphiphilic acrylates, 2-methoxyethyl acrylate up to [M](0)/[I](0)=1,000 and di(ethylene glycol) 2-ethylhexyl ether acrylate up to [M](0)/[I](0)=200, is accomplished with good control of molecular weight and molecular weight distribution in 2,2,2-trifluoroethanol at 25 degrees C using hydrazine activated Cu(0) wire as catalyst, methyl 2-bromopropionate as initiator, and Me-6-TREN as ligand. The chain end functionality of the resulting polymers has been analyzed by MALDI-TOF spectrometry to demonstrate the synthesis of perfect or near-perfect chain-end functional amphiphilic homopolymers. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 294-303