Membrane voltammetry was used to investigate composites consisting of perfluorinated MF-4SK membranes and polyaniline (PANI) and synthesized under various conditions. A theoretical analysis of the influence of transport-structure parameters of the ion-exchange membranes on their selectivity and limiting-current value is carried out. For MF-4SK/PANI composites, the increase in the exchange potential at the overlimiting state is found to be more than 2V compared to the original membrane. An analysis of how various factors influence the parameters of a current-voltage curve shows that the presence of anilinium and Fe3+ ions in the electromembrane system has no effect on the value of the potential at the onset of the overlimiting state. A phenomenological model is proposed to account for the increased plateau length at the limiting current through a change in the energetic state of water in the perfluorinated-membrane matrix resulting from the template synthesis of polyaniline.