Ionic liquids (ILs) are considered as promising solvents in aromatic extraction because of their high extractive capacities, and a large number of experimental liquid-liquid equilibrium (LLE) data can be found in the literature for systems containing hydrocarbons and ionic liquids. However, the vaporliquid equilibrium (VLE) data of {aliphatic + aromatic + IL} mixtures are scarce and essential to evaluate the feasibility of the global process. In this work, the VLE data for {n-heptane + toluene + [4empy][Tf2N]} ternary system were experimental measured at 323.2, 343.2, and 363.2 K using a headspace gas chromatography (HS-GC) technique. The selection of this ionic liquid was made taking into account its high ability to extract aromatic compounds, in order to evaluate the relationship between the extractive properties for an IL and its performance as mass agent. The experimental VLE data was successfully modeled using the non-random two liquids (NRTL) model.