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Forward osmosis membranes are an emerging technology with great potential applicability in energy-efficient wastewater treatments and the differentiation between two solutions. Such solutions often differ in their concentrations or compositions. In this study, the membrane electrical resistances of three different membranes, including cation or anion-exchange membranes and forward osmosis membranes, were analyzed by Luggin capillary coupled with AC impedance spectroscopy (EIS) so as to obtain the real membrane and ion transfer impedance values near the membrane interface. The results reveal that the membrane impedance obtained by both the DC and AC approaches decreased as the lowest external solution concentration increased. Furthermore, the relationship between the membrane conductivity and the internal salt solution concentration was also investigated. It can be seen that the external ion concentration is directly proportional to the free ion concentration in the membrane, and the free ion concentration in the membrane is closely related to the membrane electrical resistance.