The liquid-liquid equilibrium (LLE) data for the system of benzene + cyclohexane N,N-dimethyl-acetamide (DMAc) + ammonium thiocyanate were measured experimentally at 298.15 K and atmospheric pressure. All the data were correlated by the nonrandom two liquid model and they matched well. The highest selectivity coefficients of the complex solvent (DMAc + NH4SCN) can reach 12.39 at 298.15 K, which is close to that of some ionic liquids. To investigate its similarity to ionic liquids, the complex solvent was tested for electrical conductivity, and the results show that the solvent is conductive, which means there are a lot of ions in the system. The existence of ions may help to extract benzene from cyclohexane, a theory which needs to be researched further in the future.