The separation of toluene from a mixture composed of toluene and heptane was carried out in the presence of a deep eutectic solvent (DES). The DES used in this study was synthesized using choline chloride, urea and glycerol with mole ratio of 1 : 2 : 1. The liquid-liquid equilibria (LLE) of the ternary system of toluene, heptane, and DES were determined at atmospheric pressure and three temperatures of 298.2-313.2 K with an interval of 10 K. The distribution coefficients and selectivities of toluene were reported. Only a small amount of heptane was detected in the extract phase, resulting in high value of selectivity. The experimental LLE data were reasonably well correlated using non-random two-liquid (NRTL) model. The ab initio results revealed that the interactions between the DES and toluene are stronger than those between DES and heptane, which may be a reasonable explanation for the high value of selectivity in this ternary system.