Liquid-liquid phase equilibria were comparatively studied for the aqueous mixtures of propionic acid with four structurally similar aryl compounds (2-phenylethanol, 1-phenylpropanol, propiophenone, and methyl benzoate) as a function of the mixture composition at T = 298.2 K and p = 0.1 MPa. The cloud point data were measured, and the corresponding solubility diagrams for the studied ternary systems were plotted. Tie lines were measured by the analysis of both the aqueous and organic phases. All of the ternary systems display the type-1 liquid-liquid equilibrium (LLE) behavior. The quality of tie lines was confirmed by the linear behavior of the Othmer-Tobias plot. The thermodynamic model of NRTL was successfully used to correlate the experimental tie lines, and the model binary interaction parameters were determined. Evaluation of the extracting ability of the aryl solvents was performed by the estimation of the solute distribution coefficients and selectivities. Finally, all of the studied aryl solvents are appropriate separating agents for aqueous propionic acid mixtures.