βOne of the serious problem in non-aqueous redox flow batteries is redox ions crossover. Here in, the Na-β-alumina as separator was introduced and its performance evaluated using different type of electrolytes on vanadium (III) acetylacetonate charging and discharging performance in acetonitrile medium. Electrolyte type was selected based on the solution resistance using impedance analysis. Then, charging-discharging of Na-β-alumina was performed by galvanostatic mode using 0.01 mA/㎠ and 0.0015 mA/㎠ charging and discharging respectively. A columbic and voltage efficiencies were calculated using the charging-discharging data.