AbstractPrecise measurements of the viscosities of solutions of sodium polystyrenesulfonate in water and in 2‐ethoxyethanol–water mixtures containing varying amounts of 2‐ethoxyethanol have been performed at 308.15, 313.15, 318.15 and 323.15 K. The intramolecular contributions to the reduced viscosities of the polyelectrolyte solutions were obtained through isoionic dilution maintaining the total ionic strengths of the solutions at polyelectrolyte concentrations of 0.0033, 0.0054 and 0.0080 eq L−1 with sodium chloride. The Huggins constants were also obtained from the experimental data. The influences of the medium and the temperature on the intramolecular contributions to the reduced viscosities as well as on the Huggins constants have been interpreted from the points of view of the conformational characteristics and polyelectrolyte–solvent and polyelectrolyte–polyelectrolyte interactions prevailing in the polyelectrolyte solutions under investigation. Polyion chains were found to coil upon addition of 2‐ethoxyethanol to water or upon an increase of temperature. Thermodynamic affinities for polyelectrolyte–solvent and polyelectrolyte–polyelectrolyte interactions were found to depend greatly on the medium. © 2014 Society of Chemical Industry