In this study, we investigated the impedance spectra of bipolar membranes. Under the application of a reverse-biased voltage, the spectra showed a double dielectric relaxation profile due to the heterogeneous structure and it was analyzed in accordance with the three-layered dielectric model. It is defined that one of the compositions of the heterogeneous structure is situated at the membrane interface region between the negatively and the positively charged membrane with a thickness of less than several micrometers, which has an extraordinarily large electric capacity with a magnitude of sub-microfarads. It is concluded that this layer is identified with the intermediate layer in which the water splitting phenomenon occurs on the bipolar membrane.