Liquid–liquid equilibrium data are presented for mixtures of (butanenitrile (1)+acetic acid or propanoic acid or butanoic acid or 2-methylpropanoic acid or pentanoic acid or 3-methylbutanoic acid (2)+water (3)) at 298.15K. The relative mutual solubility of all the carboxylic acids is higher in the butanenitrile layer than in the aqueous layer. The influence of acetic acid and propanoic acid on the solubility of water in butanenitrile is greater than that of the other acids. Three parameter equations have been fitted to the binodal curve data. These equations are compared and discussed in terms of statistical consistency. Selectivity values for solvent separation efficiency were derived from the tie-line data. The NRTL and UNIQUAC models were used to correlate the experimental results and to calculate the phase compositions of the ternary systems. The NRTL equation fitted the experimental data far better than the UNIQUAC equation.