The aim of this work was to determine liquid-liquid equilibrium data for systems of interest in ethyl ester (biodiesel) production. The following systems were investigated: refined soybean oil + anhydrous ethanol + hexane at (313.15 +/- 0.1) K and (328.25 +/- 0.1) K, refined canola oil + anhydrous ethanol + hexane at (313.25 +/- 0.1) K and (328.15 +/- 0.1) K, and refined palm oil + anhydrous ethanol + hexane at (318.15 +/- 0.1) K and (328.25 +/- 0.1) K. The instrumental technique of near-infrared spectroscopy allied to multivariate calibration (in this work, this union was denominated "NIR method") was used for quantification of the phase compositions. The NIR method presented an appropriate experimental accuracy for quantifying equilibrium data at higher temperatures. Good reliability of the phase compositions was confirmed from values of global mass balance deviations ranging from (0.06 to 0.16)%. The experimental data were correlated using the NRTL model with an average global deviation of 0.83%.