A hydrophobically modified polyacrylamide (PAM) was synthesized by the copolymerization of acrylamide (Am) and N-hexadecylacrylamide (hAm) through solution copolymerization in a polar organic solvent. Polymer synthesis was performed in three nonaqueous media, including dimethyl sulfoxide (DMSO), a mixture of DMSO and an anionic surfactant such as sodium dodecyl sulfate, and a mixture of DMSO and an acidic surfactant such as dodecyl benzene sulfonic acid. The obtained copolymer, poly(acrylamide-co-N-hexadecylacrylamide) [poly(Am-co-hAm)], was characterized by 1H-NMR. The physical properties of poly(Am-co-hAm)s synthesized in different media were compared with those of PAM and with each other by viscosity measurement, X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. We investigated the ways in which the polymerization medium affected the hydrophobic distribution within the resulting copolymer structure. This aspect, in turn, should have altered the solution properties and the microstructure of the copolymer. For this purpose, we studied the viscometric behavior in diluted solutions, the thermal behavior and thermal stability of the copolymers, and finally, the crystalline structure of the copolymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 39939.