Abstract Copolymerization of the acrylamide-styrene system has been studied at 75°C in the absence of any conventional radical in dioxane, cyclo-hexanone, cyclohexanone/dioxane, and cyclohexanone/benzene mixtures. The reactivity coefficient values have been evaluated by YBR, KT, and EVM methods. The polarity and strong hydrogen bonding ability of the reaction medium with the amide group of the acrylamide affects the reactivity ratio values by disturbing the keto/enol equilibrium of the acrylamide. A comprehensive comparative study of the r-parameters achieved for these copolymer systems with the reactivity coefficient values of the same monomer system initiated by the conventional free-radical initiator has been presented. From the r-product values obtained by the EVM method, the following order of alternating tendency of the monomers in copolymers prepared in different media was found: cyclohexanone/benzene mixture < dioxane < cyclohexanone/dioxane mixture < cyclohexanone. The kinetic results obtained co...