AbstractThe effect of lateral substituents on the structure of the solutions and on the chain conformations ofN‐substituted andN,N‐disubstituted poly(acrylamide)s is discussed. The water‐soluble polymers show solution properties influenced by the development of strong specific interactions between the chain molecules and the solvent, and by the hydrophobicity of the substituents. In non‐aqueous solvents the interactions between the polar groups of the structural units force the polymer chains to assume unusually large unperturbed dimensions, causing the chain flexibility to depend more on the overall polarity of the molecule than on the bulkiness of the subs