The influence of organic, inorganic, and hybrid catalytic additives on the current-voltage characteristics of the bipolar region of industrial MB-1 and MB-3 bipolar membranes and analogues of an MB-2 bipolar membrane is investigated by the method of frequency spectrum of electrochemical impedance. It is shown that the introduction of compounds accelerating water dissociation reaction into the bipolar region makes it possible to obtain bipolar membranes with lower operating voltage when compared to industrial bipolar membranes.