The current trend in developing next-generation LRP systems and in particular ATRP involves reduction, elimination, and/or replacement of toxic and highly expensive catalysts and solvents with environmently friendly ones. Here, the unexpected, accelerated, ambient-temperature ATRP of methyl acrylate catalyzed by a Fe(0)/CuBr 2/Me 6TREN system in a mixture of water and inexpensive and environmentally more friendly alcohols (methanol, ethanol, and 1-propanol) is reported. The data presented open up the possibility of using fast ATRP catalyzed by a mixed transition-metal catalyst system in solvents that are inexpensive, eco-friendly, and have low boiling points. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.