The ability to do very rapid bulk atom transfer radical polymerization (ATRP) of benzyl methacrylate using a CuX/PMDETA complex at room temperature was demonstrated in this study. The experimental conditions required to synthesize low- and high-molecular-weight poly(benzyl methacrylate) with low polydispersity are reported here. The controlled/living nature of the polymerization was demonstrated through kinetic studies, and chain-extension studies. (C) 2004 Wiley Periodicals, Inc.