In order to recover the acrylonitrile from wastewater solution, liquid–liquid equilibrium behaviors in the systems {water + acrylonitrile + n-alkyl acetates} were explored at 303.2 K and 101.3 kPa., respectively. The partition coefficients and separation factors in each system were used to compare and discuss the effects of extraction. The experimental data were correlated with the NRTL and UNIQUAC models, and the binary interaction parameters required for each model were obtained. The mixing surface analysis of Gibbs energy topology was used to test the parameters in models. The UNIFAC model was used to predict LLE data compared with experimental data. The deviation between the calculated and experimental values of the three thermodynamic models was evaluated by the root mean square deviation, and the values were lower than 0.0082, 0.0088, and 0.0143, respectively. The σ-profiles were used to discuss the interactions of substances in this work.