Data of liquid-liquid equilibria (LLE) for water + 1,6-hexanediamine + 1-butanol and water + 1,6-hexanediamine + 1-pentanol ternary systems were determined at T = 298.2, 308.2, and 318.2 K under atmospheric pressure. The distribution coefficients and selectivity factors calculated from LLE data were applied to evaluate the feasibility and effectiveness of extracting 1,6-hexanediamine from the aqueous solution. The results showed that the selectivity factors decrease with the amount of 1,6-hexanediamine increasing in the aqueous phase, and the effect of temperature is insignificant in this study. The nonrandom two-liquid and universal quasichemical activity coefficient models were also applied to regress the experimental equilibrium data of the two ternary systems and the root mean, square deviation values between the correlated and experimental results were lower, than 0.7%. It turned out that these phase equilibrium behaviors can be described by the two models. Meanwhile, the binary model parameters were acquired from the relevant process simulations.