The ternary liquid-liquid equilibrium (LLE) data for cyclohexanone (CYC) + phenol + water were determined at T = (298.15, 313.15, and 323.15) K and atmospheric pressure. The distribution coefficients and separation factors were determined by the measured tie-line data, which showed the excellent performance of CYC in the extraction of phenol from aqueous solution. The reliability of LLE data was ascertained by the Bachman and Hand equations. The experimental data of the investigated ternary system were accurately correlated by the nonrandom two-liquid (NRTL) model and the universal quasi-chemical (UNIQUAC) model, and the relevant binary interaction parameters were calculated. For the NRTL and UNIQUAC models, the root-mean-square deviation values were lower than 0.6%.