Here we report a first analytical approach to determine the spectral dependence of the complex permittivity function of molecular and macromolecular ionic conductors in the interfacial layers formed by electrode polarization effects. We show that a previous model of electrode polarization effects that was successfully applied for describing the dielectric behavior of ionic liquids (Serghei, A.; Tress, M.; Sangoro, J. R.; Kremer, F. Electrode polarization and charge transport at solid interfaces. Phys. Rev. B 2009, 80, 184301) can be now generalized and applied for polymer/ionic liquid blends as well as for poly(ionic liquid)s. The determined dielectric function of the interfacial layers reveals a dramatic change in the charge transport process manifested by a large decrease in conductivity. Our approach brings the first evidence for a relaxation peak detected in the dielectric loss of the interfaces, which is attributed to an exchange process between the interface and the bulk. This study gives new insights into the mechanism of charge transport at interfaces and could thus contribute to a better correlation between the dielectric properties of ion conducting materials and their electrochemical behavior at interfaces.