Alcohols are known to promote the disproportionation of Cu(I)X species into nascent Cu(0) and Cu(II)X. Therefore, alcohols are expected to be excellent solvents that facilitate the single-electron transfer mediated living radical polymerization (SET-LRP) mediated by nascent Cu(0) species. This publication demonstrates the ultrafast SET-LRP of methyl acrylate initiated with bis(2-bromopropionyloxy)ethane and catalyzed by Cu(0)/Me-6-TREN in methanol, ethanol, 1-propanol, and tert-butanol and in their mixture with water at 25 degrees C. The structural analysis of the resulting polymers by a combination of H-1 NMR and MALDI-TOF MS demonstrates the synthesis of perfectly bifunctional alpha,omega-dibromo poly(methyl acrylate)s by SET-LRP in alcohols. Moreover, this work provides an expansion of the list of solvents available for SET-LRP. (c) 2008 Wiley Periodicals, Inc.