Polymerization of methyl acrylate (MA) catalyzed by Cu(0) is carried out in toluene using a range of alcohols and phenol as additives to facilitate the reaction. The polar/coordinating additives promote disproportionation of Cu(I) to Cu(0), the proposed active species in single electron transfer living radical polymerization (SET-LRP), and Cu(II) whilst toluene maintains solubility of the reagents and products. In this work, the use of alcohols as additives is optimized. Polymerizations are monitored in real time using rapid chromatography to obtain conversion and molecular weight distribution data without the necessity of manual sampling. Rapid gel permeation chromatography with low angle laser light scattering detection is shown to be a viable method of obtaining molecular weight distribution data in real time compared with conventional analytical techniques. Moreover, the changes in CuBr2 concentration during SET-LRP reactions are monitored online using a photodiode array detector. Finally, the kinetics of SET-LRP of MA using an ultra pure highly porous Cu(0) is performed and a detailed discussion on the role of Cu(II) is provided. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:1753-1763, 2011