The present work describes a combination of microwave irradiation as a heating source and water as a solvent for carrying out a living/controlled polymerization of acrylamide. Reasonable results were obtained for a nitroxide-mediated radical polymerization (NMP) with a combination of a conventional hydrosoluble radical initiator and a beta-phosphonylated nitroxide. The microwave enhancement of the polymerization was found to depend oil the mode of irradiation, i.e., either a dynamic (DYN) mode or an pulse (SPS) mode. The Former mode corresponded to a dynamic control of the temperature by way of a high initial microwave power, and in this case, no specific microwave effect was observed. Oil the other hand, in the SPS mode, which is a pulsed power mode, the result showed a strong acceleration of the polymerization process (>50 times) without the loss of the living/controlled polymerization characteristics, which is relevant with a reinitiation of the polyacrylamide macroinitiator even after 100% of conversion. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A Polym Chem 47 6919-6931, 2009