Liquid-liquid equilibria of the quaternary system of methyl oleate, glycerol, hexane, and methanol were experimentally quantified at room temperature and atmospheric pressure. UNIFAC and Modified UNIFAC activity coefficient models were used to predict the properties of the coexisting phases at equilibrium. These models used the previously reported binary group interaction parameters without any regression. Overall, the predicted tielines showed no significant lack of fit when compared to the experimental tielines for both models; however, the precision of the experimental data was insufficient to verify achievement of the ASTM standard for the glycerol content of the methyl oleate-rich phase. Nevertheless, the hexane-methanol solvent system showed potential to achieve the required separation.