Ternary liquid-liquid equilibria (LLE) data in systems involving ionic liquids has been investigated by several years, mainly due to the innovative role of ionic liquids as extraction solvents. The thermodynamic modeling of these systems has been performed almost invariably with the well-known NRTL model. In recent years, the UNIQUAC model has also been used, with structural parameters for ionic liquids determined either by empirical correlations or, more recently, through quantum mechanics calculations. In this work, the structural group volume and area parameters for the group-contribution UNIFAC method have been calculated for six ionic liquids following the quantum mechanics approach. The Density Functional Theory (DFT) was used to optimize the molecular geometry and the Polarizable Continuum Method (PCM) was used to calculate the area and volume. The obtained parameters were used to correlate LLE data for twenty-four ternary systems, totalizing 169 tie-lines. New interaction parameters were also estimated between the solvent and ionic liquid functional groups. The results are very satisfactory, with root mean square deviations between experimental and calculated compositions about 1.6%. (C) 2010 Elsevier B.V. All rights reserved.