The separation of toluene and dimethyl carbonate azeotropes is beneficial for resource recovery and environmental protection. Ionic liquids (ILs) are widely considered as a green solvent. The feasibility of separating the toluene and dimethyl carbonate mixtures with pinch point using 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6]), 1-buty1-3-methylimidazolium dicyanamide ([Bmim][DCA]), and 1-ethyl-3-methylimidazolium dicyanamide ([Emim] [DCA]) as solvents are investigated in this work. The ternary liquid-liquid equilibrium data of toluene + dimethyl carbonate + ILs are determined at 298.15 K under 101.325 kPa. The distribution coefficient (beta) and selectivity (S) are used to evaluate the extraction performance of ILs. The selectivity at the infinite-dilution activity coefficient (S-dimethyl(infinity) (carbonate, toluene)) based on conductor like screening model (COSMO-SAC) is compared with the selectivity calculated from the experimental data. Interaction relationship among toluene, dimethyl carbonate, and ILs are studied based on sigma-profiles and bond energy. The binary interaction parameters of nonrandom two-liquid Nationally Recognized Testing Laboratory and universal quasichemical models are well-regressed from the experimental data.