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The liquid-liquid equilibrium for the quaternary system of o-xylene, water, butyric acid, and 1-butanol was measured at 298.15 K and atmospheric pressure. Binodal curves, tie-lines, a distribution, and a selectivity for the quaternary system were determined to investigate the effect of binary solvents, o-xylene and 1-butanol, on the extraction of butyric acid from aqueous solution. Tie-line compositions were correlated using Othmer-Tobias and Hand methods. In addition, these experimental tie line data were also compared with the values predicted by the UNIFAC model. In this study, the UNIFAC model was capable of predicting the compositions of this quaternary system within an average RMSD of 5.08 mol%.