The effect of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid on the living radical polymerization of methyl methacrylate initiated with arenesulfonyl chlorides and catalyzed by the self-regulated Cu2O/2,2'-bipyridine catalyst was investigated. A dramatic acceleration of the living radical polymerization of methyl methacrylate in this ionic liquid was discovered. This accelerated living radical polymerization maintained an initiation efficiency of 100%, eliminated the induction period of this catalyst, and produced poly(methyl methacrylate) with molecular weight distribution of 1.1 and perfect bifunctional chain-ends. The kinetic analysis of the living radical polymerization in the presence of ionic liquid demonstrated a rate constant of propagation that follows an almost first order of reaction on the ionic liquid concentration and therefore, the ionic liquid exhibits catalytic effect. The catalytic effect of the ionic liquid facilitated the reduction of the catalyst concentration from stoichiometric to catalytic and allowed the decrease of the polymerization temperature from 80 to 22 degrees C. (c) 2005 Wiley Periodicals, Inc.