Liquid-liquid equilibria (LLE) data play an important role in the project and design of separation processes. The aim of this work was to study the LLE data of the solubility (binodal) curves and tie-lines for the glycerol (1) + ethanol (2) + coconut biodiesel (3) system at two different temperatures [(293.15 and 323.15) K], at atmospheric pressure. From the experimental data, it could be observed that the relative mutual solubility of ethanol is higher in the glycerol phase than the biodiesel phase. A consistency analysis has been performed by using the Othmer-Tobias correlation. The experimental liquid-liquid data were correlated by using two local composition models (NRTL and UNIQUAC) for the activity coefficient calculation. From these models, binary parameters have been determined. Distribution coefficients and separation factors were measured to evaluate the extracting capability of the ethanol used as a solvent.