(Vapor + liquid) equilibrium (VLE) data for ternary systems of (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), (1-hexene + cyclohexane), and (1-hexene + benzene) with an ionic liquid were measured by headspace gas chromatography. The applied ionic liquid 1-methyl 3-octylimidazolium thiocyanate, [Omim][SCN], acts as an entrainer. The comparison of the measured VLE data with the equilibrium data for the binary mixtures without ionic liquid show that [Omim][SCN] significantly improves the separation factor of these systems. The NRTL thermodynamic model is applied for correlating the experimental data. The modeling results show the NRTL model can correlate the experimental data with (C) 2012 Elsevier Ltd. All rights reserved.