Electrolytic conductivity behavior of some cationic polysaccharides in water, methanol, and the mixtures water/methanol is presented. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-alkyl-N,N-dimethyl-2-hydroxypropyleneammonium chloride, attached to a dextran backbone. This study considers the influences of polymer concentration (1 x 10(-6) < C < 1 x 10(-2) monomol L-1) and the charge density (xi = 0.48-3.17) modified either by changing charge distance (b) or dielectric constant of the solvent (epsilon) on polyion-counterion interaction in salt-free solutions. Above the critical value, xi(c) = 1, the variation of the equivalent conductivity (Lambda) as a function of concentration is typical for a polyelectrolyte behavior. The conductometric data in water were analyzed in terms of the Manning's counterion condensation theory. The presence of longer alkyl chains at quaternary N atoms was found to have a negligible influence on the Lambda values. The results show that the decrease of the medium polarity results in the decrease of the number of free ions and, consequently, of the equivalent conductivity values. (c) 2005 Wiley Periodicals, Inc.