Liquidliquid equilibrium (LLE) data for the ternary system water + benzyl alcohol + benzaldehyde were measured at (303.2 to 343.2) K under atmospheric pressure. The reliability of the experimental LLE data were checked by the OthmerTobias and the Hand correlations. The experimental data were correlated by both the (nonrandom two liquid) NRTL and the universal quasichemical activity coefficient (UNIQUAC) models. The relative-mean-standard deviations obtained are 0.16 % by the NRTL model and 0.14 % by the UNIQUAC model. The relevant model interaction parameters were regressed with the experimental data. The distribution coefficients and separation factors were used to discuss the ability of the solvent water to extract benzyl alcohol from binary benzyl alcohol + benzaldehyde solvent mixtures. The results show that the separation factor of benzyl alcohol increased with an increase of the mass of water and decreased with an increase of temperature, which indicates that the extraction separation of benzyl alcohol from binary benzyl alcohol + benzaldehyde mixtures by the extract agent water may be feasible. The obtained results might be used in the separation process for the ternary system water + benzyl alcohol + benzaldehyde.