In order to screen ionic liquids (IL) as suitable solvents for the separation of benzene and cyclohexane, the extraction efficiency of ILs (12 cations and 22 anions) was estimated based on COSMO-RS predictions of infinite dilution activity coefficients of benzene and cyclohexane in different ILs..[C(4)mim][AlCl4] was found to be the most promising solvent. To provide deep insight on how the IL structure influences the extraction efficiency, molecular interactions between IL ions and benzene were determined from DFT calculations. Moreover, liquid-liquid equilibrium data of the ternary system benzene-cyclohexane-[C(4)mirn][AlCl4] were experimentally determined and used to fit parameters of the NRTL activity coefficient model. Based on the NRTL model the continuous extraction process was simulated and compared with a reference process using sulfolane as solvent. For the extraction process using [C(4)mim][AlCl4], high cyclohexane product purity (99.65 wt%) and high benzene recovery efficiency (98.03%) can be reached with at much lower energy consumption and higher product yield compared to conventional extraction solvents. In conclusion, the ionic liquid [C(4)mim][AlCl4] is a promising solvent for the extractive separation of benzene and cyclohexane. (C) 2014 Elsevier Ltd. All rights reserved.