Radical polymerization of N-methylacrylamide (NMAAm), N,N-dimethylacrylamide (DMAAm), and N-methyl-N-phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereo specificity of the radical polymerization of acrylamide derivatives depended on the N-substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534-6539, 2009