Recently, the study about the use of ionic liquids (ILs) in the aromatic extraction is focused in the selective separation of the hydrocarbons and the solvent in order to propose a whole alternative process involving ILs. As a consequence, the vapor liquid equilibria (VLE) for the hydrocarbons + ILs systems are required. In this work the VLE for several alkane + toluene systems in the presence of the 1-ethyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide ([4empy][Tf2N]) (0.3) + 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) (0.7) binary IL mixture were determined. In addition to extend the experimental VLE information, this work is aimed at the alkane structure evaluation: linear alkanes (n-hexane and n-octane), cyclic alkanes (cyclohexane), and branched-chain alkanes (2,3-dimethylpentane) have been used. All systems have been studied at 323.2, 343.2, and 363.2 K over the whole range of composition within the miscibility region. The NRTL thermodynamic model was used to adjust the VLE for all systems. The high values of alkane/toluene relative volatilities found suggest the alkane selective separation from the reference aromatic hydrocarbon, toluene.