Liquid−liquid equilibria for the ternary systems water + acetic acid + ethyl acetate and water + acetic acid + isophorone (3,5,5-trimethyl-2-cyclohexen-1-one) were measured over the temperature range (283 to 313) K. The results were used to estimate the interaction parameters between each of the three compounds of the systems studied for the NRTL and UNIQUAC models. The estimated interaction parameters were successfully used to predict the equilibrium compositions by the two models; experimental data were successfully reproduced. The UNIQUAC model was the most accurate in correlating the overall equilibrium composition of the studied systems. Also the NRTL model satisfactorily predicted the equilibrium composition. Isophorone experimentally resulted in a better extraction capacity for acetic acid and in a lower miscibility with water.