The objective of this work was to explore the feasibility of four ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium bis{(trifuoromethyl)sulfonyl}imide, [EMIM][NTf2], 1-allyl-3-methylimidazolium bis{(trifuoromethyl)sulfonyl}imide, [AMIM][NTf2], 1-benzyl-3-methylimidazolium bis{(trifuoromethyl)sulfonyl}imide, [BzMIM][NTf2], and 1-butyl-4-cyanopyridinium bis{(trifuoromethyl)sulfonyl}imide, [(BCNPY)-P-4][NTf2] for the separation of ethylbenzene/styrene compounds. The liquidliquid equilibrium (LLE) in ternary systems of {IL(1) + styrene (2) + ethylbenzene (3)} at T = 298.15 K and ambient pressure are presented. The final chromatography analysis has shown that the studied ILs have not been found in the raffinate phase, which is very convenient for new technology. The effect of IL cation was examined with respect to the selectivity and solute distribution ratio of styrene extraction. The comparison of different ILs is presented in the studied separation problem. It was observed that the best separation effectiveness has [EMIM][NTf2] in comparison with other studied ILs in this work but lower than [EMIM][DCA] presented previously by us. The experimental tie-lines were correlated with the non-random two liquid NRTL model. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.