The impedance spectra of two systems of multi -phase polymeric electrolyte were studied' One system consisted of LiClO4 doping polyethylene glycol polyurethane which was characterized by bi -ionic conductor and the another system was based ona sulfonated polyurethane ionomer with single-ion transportation character. An equivalent circuit of alternating impedance measurement system for the multi-phase polymeric electrolytes was proposed. The ionic conductivity and other fundamental electricity parameters were respectively by resolving of impedance spectra with computer fitting analysis and of the dispersion relations of boundary impedance.Based on the two methods the calculated ionic conductivities came to an unanimous conclusion in spite of the difference in transport numbers of cation of the two samples.The impedance spectra of the different samples can be interoreted with the equivalent circuit suggested by the present paper.