The Cu(0)/Me-6-TREN-catalyzed single-electron transfer mediated living radical polymerization (SET-LRP) of methyl acrylate in the presence of the classic 4-methoxyphenol free radical inhibitor was investigated. Kinetic experiments, combined with H-1 NMR, and MALDI-TOF MS analysis of the resulting polyacrylates demonstrated that SET-LRP is a robust synthetic method that does not require the purification of the monomers to remove the radical inhibitor. It is anticipated that these results will contribute to the expansion of technological and fundamental applications of SET-LRP since it allows the synthesis of polymers with a structural perfection that previously was not accessible by any other method, starting from unpurified monomers, solvents, initiators, and ligands. (C) 2008 Wiley Periodicals, Inc.