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Alkaline water electrolysis (AWE) refers to a representative water electrolysis technology that applies electricity to synthesize hydrogen gas without the production of carbon dioxide. The ideal polymer electrolyte membranes for AWE should be capable of transporting hydroxide ions (OH−) quickly in harsh alkaline environments at increased temperatures. However, there has not yet been any desirable impedance measurement method for estimating hydroxide ions’ conduction behavior across the membranes, since their impedance spectra are significantly affected by connection modes between electrodes and membranes in the test cells and the impedance evaluation environments. Accordingly, the measurement method suitable for obtaining precise hydroxide ion conductivity values through the membranes should be determined. For this purpose, Zirfon®, a state-of-the-art AWE membrane, was adopted as the standard membrane sample to perform the impedance measurement. The impedance spectra were acquired using homemade test cells with different electrode configurations in alkaline environments, and the corresponding hydroxide ion conductivity values were determined based on the electrochemical spectra. Furthermore, a modified four-probe method was found as an optimal measurement method by comparing the conductivity obtained under alkaline conditions.