Liquid liquid equilibrium (LLE) data for the ternary (water + (+/-)alpha-phenylethylamine + n-hexane) system were obtained experimen, tally at T = 298.2, 318.2, and 333.2 K, respectively, and atmospheric pressure by gas chromatography for the first time. The binodal curve data at 333.2 K was determined rising the cloud point method. The system exhibits two-liquid-phase-coexisting at 333.2 K while it presented the state of three two-liquid-phase-coexisting, regions and one three-liquid-phase-coexisting region in the triangle phase diagram at 298.2 and 318.2 K. Separation factor was calculated to evaluate the extraction efficiency of this system. Correlation of the experimental tie lines was conducted through the me of the NTRL and UNIQUAC equation, which provides good correlation of the experimental data.