The atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA), using alpha,alpha'-dichloroxylene as initiator and CuCl/N,N,N',N",N"-pentamethyl-diethylenetriamine as catalyst was successfully carried out under microwave irradiation (MI). The polymerization of MMA under MI showed linear first-order rate plots, a linear increase of the number-average molecular weight with conversion, and low polydispersities, which indicated that the ATRP of MMA was controlled. Using the same experimental conditions, the apparent rate constant (PPP) under MI (k(p)(app) = 7.6 x 10(-4) s(-1)) was higher than that under conventional heating (k(p)(app) = 5.3 X 10(-5) s(-1)). (C) 2004 Wiley Periodicals, Inc.