Poly(methyl acrylate)s, poly(ethyl acrylate)s, and poly(butyl acrylate)s with a,c)-di(bromo) chain ends and Mn from 8500 to 35,000 were synthesized by single-electron-transfer living radical polymerization (SET-LRP). The analysis of their chain ends by a combination of H-1 and 2D-NMR, GPC, MALDI-TOF MS, chain end functionalization, chain extension, and halogen exchange experiments demonstrated the synthesis of perfectly bifunctional polyacrylates by SET-LRP. (c) 2007 Wiley Periodicals, Inc.