The atom transfer radical polymerization of butyl methacrylate (BMA) under microwave irradiation (MI) was successfully carried out, using (1-Chloroethyl) benzene as initiator and CuCl/2,2′-bipyridine as catalyst. The results showed that microwave could apparently accelerate the rate of polymerization, under the same experimental conditions; the apparent polymerization rate (kpapp) was 34 times under microwave irradiation than that under conventional heating. In addition, the effects of the concentration of initiator and catalyst and the solvent were studied. Poly (butyl methacrylate) with narrow polydispersity and anticipated molecular weight was obtained.