AbstractThe complexation of poly(4‐vinylpyridine)(1), poly(2‐methyl‐5‐vinylpyridine)(2)and poly(2‐vinylpyridine)(3)with bromides, perchlorates and tetraphenylborates of alkali metals in organic solvents was investigated by means of electroconductivity, viscometry and nuclear magnetic resonance spectroscopy. The influence of the nature of the polymer, the low‐molecular‐weight salt and the solvent, salt and polymer concentration as well as the temperature on complexation was studied. The fraction of cations and that of polymer units bound were determined. The compositions of the complexes were found by means of viscometry. It was established that the mechanism of binding of the polymers with alkali metal salts is of the io