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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)/Me₆‐TREN in methanol, ethanol, 1‐propanol, and tert‐butanol and in their mixture with water at 25 °C. The structural analysis of the resulting polymers by a combination of ¹H NMR and MALDI‐TOF MS demonstrates the synthesis of perfectly bifunctional α,ω‐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. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2745–2754, 2008