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The living radical polymerization of methyl methacrylate initiated from sulfonyl chlorides and catalyzed by the new catalytic systems Cu₂Y/Bpy and CuY/Bpy, where Y is O, S, Se, or Te and Bpy is 2,2′‐bipyridine, is described. An induction time was observed in all polymerization experiments. The values of the experimental rate constants of polymerization (k_p ^exp) increased whereas the corresponding induction times decreased in the order Y = O < S < Se < Te. For the entire series of catalysts, k_p ^exp for CuY was less than k_p ^exp for Cu₂Y. A mechanistic interpretation that involves the in situ generation of the CuCl/CuCl₂ pair, starting from Cu₂Y or CuY, is provided. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3839–3843, 2000