In this work, the selective separation of toluene from mixtures of toluene + heptane or toluene + hexane was investigated using the newly emerging family of solvents, namely, deep eutectic solvents (DESs), as the extracting agent. The liquid liquid equilibria (LLE) of these systems were measured at a temperature of 303.2 K and a pressure of 85 kPa. The DESs considered were made of choline chloride as the hydrogen bond acceptor (HBA) and phenol as the hydrogen bond donor (HBD), at the two different HBA-HBD molar ratios of 1:3 and 1:4. The experimental liquid-liquid equilibrium data, along with the selectivities and distribution coefficients, were reported for each set of equilibrium data and also compared with other ternary systems in the literature containing toluene + heptane or toluene + hexane and various solvents. The experimental results revealed that the studied DESs in this work have the potential to be utilized in the separation of toluene from either hexane or heptane at low concentrations of toluene. The experimental LLE data was also modeled using the nonrandom two-liquid (NRTL) model. The values of the root mean-square deviations of the NRTL results with respect to experimental values indicated acceptable agreement, suggesting NRTL as a potential model for such systems.