Abstract Diffusion of non-associated electrolytes (potassium chloride and lithium chloride) in concentrated aqueous solutions (0.1–1.0 mol dm −3) has been studied in hydrogels derived from acrylamide and methyl methacrylate to study the mechanism of electrolyte transport. The preparation of two gels with different monomer ratio compositions resulted in obtaining membranes of substantially different hydrophilic character with polymer fractions of 0.3 and 0.5. Cukier hydrodynamic model was applied to explain the dependence of the diffusion coefficients of KCl and LiCl on the electrolyte concentration in hydrogel obtained experimentally. It was shown that the increase of the diffusion coefficients is accompanied with a decrease of the mean distance of approach of the ions. This can be explained by the formation of ion-pairs, resulting in a further contribution to diffusion once there is a decrease in the hydrodynamic resistance of the medium to the diffusing particles. Parameters, which characterise such a behaviour quantitatively, are different for different electrolytes and depend on water content in the gel.