The effects of polycation structure, counterions and the nature of the solvent on the interaction between low-molecular-weight salts with some cationic polyelectrolytes in water and methanol were investigated. The polyelectrolytes used in this study were cationic polymers with quaternary nitrogen atoms in the backbone with or without a nonpolar side chain (polymer type PCA5H1, PCA5D1 and PCA5) or tertiary amine nitrogen atoms in the main chain (polymer type PEGA). LiCl, NaCl, KCl, NaBr, NaI and Na2SO4 were used as low-molecular-weight salts. The interaction between polycations and salts was followed by viscometric and conductometric measurements. The study of the interaction of monovalent counterions with cationic polyelectrolytes emphasized an increase in the interaction with the decrease in the radius of the hydrated counterion, both for strong polycations and for weak polycations, suggesting that counterion binding is nonspecific. In the case of SO2− 4 anions, the Λm− c1/2 curve passes through a minimum at cp values between 1 × 10−3 and 3 × 10−3 unit mol/l; this phenomenon can be explained by the maximum counterion interaction owing to the capacity of the polyvalent counterion to bind two charged groups by intra- or interchain bridges. The investigation of the influence of the polycation structure on the counterion binding indicated an increase in charged group–counterion interactions with a decrease in the nonpolar chain length and an increase in the quaternary ammonium salt group content (charge density) in the chain. The polyelectrolyte with tertiary amine groups in the chain, PEGA, showed, on one hand, a cation adsorption order as K+>Na+>Li+ and, on the other hand, a stronger association between ions and PEGA chains in methanol than in water owing to the poorer solvating effect of methanol on the cations. [ABSTRACT FROM AUTHOR]