A radical polymerization process that yields well-defined polymers normally obtained only through anionic polymerizations is reported. Atom transfer radical polymerizations of styrene were conducted with several solubilizing ligands for the copper(l) halides : 4,4’-di-tert-butyl, 4,4’-di-n-heptyl, and 4,4’-di-(5-nonyl)-2,2’-dipyridyl. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities (ratio of the weight-average to number-average molecular weights of 1.04 to 1.05). Similar results were obtained for the polymerization of acrylates.