The complex electrochemical impedance spectra of tungsten – (KCl-LiCl) interface at 700–800°C consist of two well-separated semicircles. One at high frequencies and reflects charge transfer resistance and interfacial capacitance. The second is at low frequencies and is attributed to the electrical properties of the melt. Similar spectra are measured for tungsten – (KCl-NaCl) interface. The low-frequencies semicircle though is reduced above 750°C. Entropy estimations from cyclic voltammetry measurements indicate an increase in the entropy of KCl-NaCl at ∼750°C and a possible change in the inter-ionic order and interactions. Asymmetric anion polarization interactions are suggested to be involved.