Ionic liquids have become one of the growing “green” media for engineers due to their remarkable physicochemical properties. The applications of these solvents in extraction processes have been extensively investigated and reviewed. This paper reports the ability of the ionic liquid (IL), 1-butyl-3-methylimidazolium methyl sulfate [BMIM] [MeSO4] to act as an extraction solvent in petrochemical process for the removal of heptane from its azeotropic mixture with ethanol. The suitability of [BMIM] [MeSO4] is assessed by means the experimental liquid–liquid equilibrium (LLE) for the ternary system heptane+ethanol+[BMIM] [MeSO4] at 298.15K. The solute distribution ratio, the selectivity and the extraction factor suggest the efficiency of the IL used like solvent. A comparison with other IL, in terms of solvent capacity, is enclosed. As design of a separation process requires knowledge of the phase equilibria, NRTL equation is employed to correlate LLE data. Extraction process with this solvent is simulated using conventional software and the obtained results are shown. Experimental data are obtained in a laboratory-scale packed column extraction system for the separation of this azeotropic mixture using [BMIM] [MeSO4]. A comparison between the experimental column data together with simulated report are enclosed.