This paper describes the use of electrodes modified with poly(pyrrole-viologen) films as electroreleasing devices. Dicationic viologen (4,4’-bipyridinum) units (V2+) confer anion exchange properties on these polymer films. Furthermore, charge transfer interactions take place between V2+ groups and pi donor molecules. Viologen groups can be reduced reversibly in two separate one-electron steps to form V+. and then V0. This allows electrochemical modulation of the anion exchange capacity and the pi acceptor character of the polymer films. Extraction and electrochemically controlled release of redox-active metal complexes and organic anions (Mo(CN)8(4-), Fe(CN)8(3-), ABTS) has been studied to evaluate the exchange capacity and the electroreleasing properties of these systems in both organic and aqueous electrolyte. Biomolecules have also been incorporated and released in quantifiable amounts without loss of their biological activity.