Biodiesel has many advantages because it is a biodegradable, nontoxic fuel and its production results in less particulate matter. For this reason it has been studied in many fields of science as a substitute for mineral fuels. Short chain alcohols such as ethanol have been used for extraction of soybean and sunflower biodiesel in the literature. The present paper reports liquid–liquid equilibrium data for systems containing soybean biodiesel + glycerol + ethanol at (293.15 and 323.15) K and sunflower biodiesel + glycerol + ethanol at (298.15 and 313.15) K. Binodal curves were obtained by the cloud-point method, while tie-line compositions were obtained by density measurements. The values of distribution coefficients and selectivities indicate that the ethanol is a good solvent for the extraction of soybean biodiesel and sunflower biodiesel from glycerol. The reliability of experimentally measured tie-line data can be ascertained by applying the Othmer–Tobias equation. The experimental data were correlated by the nonrandom two-liquid (NRTL) model, using the simplex minimization method with a composition-based objective function. The results found in this work were considered satisfactory, by analyzing statistical parameters using root-mean-square deviations.