Considering vegetable oils as complex multi component mixtures composed of triacylglycerols (TAGs), diacylglycerols (DAGs), and monoacylglycerols (MAGs) in liquid liquid extraction, as deacidification or another purification technique, it is crucial not only to describe the process, but also the oil enrichment in DAG content, or the obtainment of MAG-rich products, as emulsifiers. This study aimed to attain the liquid liquid equilibrium (LLE) data of systems composed of TAG of refined oils (soybean, cottonseed, and rice bran) + DAG + MAG + ethanol at T = 303.2 and 318.2 K. The components presented in the liquid phases in equilibrium (TAG, DAG, MAG, and ethanol) were quantified by high-performance size-exclusion chromatography (HPSEC). The preference of DAG for the oil-rich phase and of MAG to the solvent-rich phase is consistent to data reported in the literature. The average deviation between experimental and calculated compositions was less than 0.57% using the NRTL model and up to 6.21% using the original version of the UNIFAC model with two parameters set.