Poly-[1-methyl-3-(pyrrol-1-ylmethyl)pyridinium] chloride films on glassy carbon electrodes greatly increased the voltammetric peak currents of anthraquinone-2,6-disulfonate, anthraquinone-2-sulfonate, and 5,5’-indigodisulfonate ions. This electrocatalytic action of the polymer film is attributed to the effective extraction of the anions from very dilute solutions; a partition coefficient of similar to 2 x 10(4) in 0.1 M NaCl solutions was evaluated from the coulometric data for anthraquinonesulfonates bound within the film. The merit of the polycationic film is to some extent counteracted by poor electronic conduction of the polymer and slow ion transport through the film; the diffusion coefficients of the anions were found to be of the order of (3-8) x 10(-10) cm(2) s(-1) by linear sweep voltammetric and chronopotentiometric measurements. A decrease in partition coefficient with increasing concentration of NaCl in solution indicates that an electrostatic attraction dominates the binding of anions to the polymer. However, the order of the partition coefficients for organic anions cannot be rationalized solely in terms of the magnitudes of their negative charges. A great influence of 1-propanol added to solutions on the partition coefficient suggests that an additional factor affecting the distribution equilibria seems likely to be hydrophobic interaction between the polymer film and incorporating ions.