Experimental solubility curves and tie-line compositions were comparatively investigated for the aqueous mixtures of acetic acid with three structurally similar aryl carbonyl compounds (propiophenone, acetophenone, and methyl benzoate) at (298.2 and 308.2) K and 101 kPa. The studied ternary mixtures display type-1 phase behavior. The correlation of the measured tie lines was performed by the NRTL and UNIQUAC models. The model binary interaction parameters were obtained by measured tie-line values and minimizing an objective function. The consistency of the NRTL parameters was validated through topological analysis connected to the Gibbs tangent principle and stability test. Evaluation of the capacity of each solvent was performed using the calculation of distribution coefficients and separation factors. Distribution coefficient (constant) and selectivity (separation factor) values were evaluated over the immiscibility region using the experimental equilibrium data. The influence of extraction temperature on the immiscibility region was found to be minor.