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The complex Cu(I)Cl/4,4‘-dinonyl-2,2‘-bipyridine (bpy9) catalyzes via a redox process the homogeneous “living” radical polymerization of styrene(s), methacrylates, and acrylates initiated with a variety of functional phenylsulfonyl chlorides. Polymers with narrow molecular weight distribution and molecular weights close to the theoretical ones are obtained from these three classes of monomers. Kinetics of propagation and initiation were performed with selected substituted phenylsulfonyl chlorides and with their monoadducts to monomer. Polymerizations follow first-order kinetics internally in monomer and externally in Cu(I)Cl while initiation is first order internally in initiator and in Cu(I)Cl concentrations. A catalyst concentration dependence of the optimum bpy9/Cu(I)Cl ratio which yields the largest rate constant of polymerization was observed. The apparent rate constants of propagation corrected for catalyst …