In this work, ternary liquid liquid equilibrium (LLE) data for the castor oil biodiesel (BIO-CO) + ethanol + glycerol and quaternary LLE data for biodiesel (BIO-CO) + ethanol + glycerol + NaOH systems at (298.2 and 333.2) K and atmospheric pressure (approximate to 95 kPa) were determined by gas chromatography. The influence of temperature and catalyst in the phase diagrams were studied. Ethanol partition coefficients and biodiesel selectivities were calculated. Results showed that ethanol distributed slightly more to the glycerol phase and that biodiesel solubilizes preferentially ethanol than glycerol. LLE experimental data were correlated with the NRTL model, presenting root-mean-square deviations < 1.3 %. Hand and Othmer-Tobias correlations were used to test the data quality, which presented R(2) > 0.98 for all systems.