The present work reports liquid-liquid equilibrium data for the systems containing refined rice bran oil + anhydrous ethanol + water + hexane at (298.15 +/- 0.2) K with mass fractions of (4.14, 9.84, and 14.79) % of water in anhydrous ethanol and at (313.15 +/- 0.2) K with a mass fraction of 4.40 % of water in anhydrous ethanol. The instrumental technique of near-infrared spectroscopy allied to multivariate calibration (in this work, termed "NIR method") was used for determination of the phase compositions. To avoid phase separation in sampling for the system at 313.15 K, the phase samples were diluted with tetrahydrofuran. The results were evaluated by calculation of the global mass balance, resulting in relative deviations lower than 0.5 % to all systems studied in this work. The experimental data were correlated using the NRTL model, and for all systems, the global deviation was less than 1.0 %. These results indicate the good quality of the experimental data and that the NIR method gives good results even when the components have a low mass fraction in the mixture.