Mutual solubility of propane-1,2,3-triol with pentane, hexane, heptane, or ethyl acetate and mutual solubility between different vegetable oils (sunflower oil, soybean oil, corn oil, and olive oil) with methanol or ethanol have been reported at temperatures ranging from (298.2 to 348.2) K and atmospheric pressure. Furthermore, the binodal curves for ethyl acetate + methanol or ethanol + propane-1,2,3-triol at (303.2, 313.2, and 323.2) K have been explored. A higher solubility has been found in the system containing ethanol than the system containing methanol. The GCA-EoS model has been used to represent these mixtures. The distribution coefficient of alcohol and the selectivity of propane-1,2,3-triol in the ternary mixture of ethyl acetate + methanol or ethanol + propane-1,2,3-triol have been evaluated by GCA-EoS model. These results indicate a more effective use of propane-1,2,3-triol as separation agent by liquidliquid extraction in the binary mixture of ethyl acetate + methanol than ethyl acetate + ethanol. On the other hand, regarding the mixtures containing vegetable oil, the mutual solubility of alcohol in the phase rich in vegetable oil is bigger than the mutual solubility of vegetable oil in the phase rich in alcohol.