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Separation among rubidium and potassium ions from salt lake brines remains challenging. In this work, a typical room temperature ionic liquid 1-ethyl-3-metyhlimidazaolium bis(trifluoromethylsulfonyl)imide ([C2mim+][NTf2–]) was used as diluent and synergistic extractant, dicyclohexano-18-crown-6 (DCH18C6) was used as extractant to extract rubidium ions from brine solutions which contain high concentrations of potassium ions was investigated. Under the optimal conditions, the single extraction efficiency of rubidium ions was up 93.63%. The thermodynamic parameters of the rubidium ion extraction were obtained. Based on the slope analysis method, the extracted species in the organic phase were ascertained as 1:1 complex. UV-visible has been performed to investigate the ion concentration of ionic liquid before and after the interaction of metal ions and ligands. Rubidium ions in [Rb · DCH18C6]+ complex were stripped by 2.5 mol · L–1 NH4NO3. The extraction system offers high efficiency, simplicity and environmentally friendly application prospect to separate rubidium from brine solutions.