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The separation of Li⁺ and [Bmim]⁺(1-Butyl-3-methylimidazolium) using a cation exchange membrane in an electric field is studied in this work. The effects of the type of cation exchange membrane, current density, total cation concentration, temperature, and anion types on the separation efficiency are investigated. The results indicate that it is feasible to achieve the efficient separation of Li⁺ and [Bmim]⁺ using the selectivity of cation exchange membranes under an electric field. The CIMS membrane (a type of cation exchange membrane produced by ASTOM Corporation) shows obvious selectivity of Li⁺ from [Bmim]⁺. When the current density is 5 mA/cm² and the feed concentrations of Li⁺ and [Bmim]⁺ are 0.3 mol/L and 0.2 mol/L, respectively, the selective transport coefficient of CIMS can reach 5.9 in the first 120 min of the process. The separation efficiency can be effectively improved by reducing the current density and increasing the total cation concentration. Decreasing the feed temperature can slightly improve the separation efficiency. Changing the type of anion in the feed from chloride to acetate has no detectable effect on the separation.