Nitroxide-mediated polymerization is shown to produce well-defined poly( N, N -dimethylacrylamide) samples. In the presence of SG1, a β-phosphonylated nitroxide, the free radical polymerization of N, N -dimethylacrylamide indeed exhibits a “living”/controlled character, provided the nitroxide is used in excess and its concentration finely tuned as compared to that the free radical initiator (AIBN). Poly( N, N -dimethylacrylamide- b -butyl acrylate) diblocks copolymers were subsequently derived by sequential polymerization of the two corresponding monomers.