Liquid-liquid equilibria (LLE) experimental data for the systems of vinyl acetate + acetic acid/ethanol + water were determined at temperatures of 298.15 and 308.15 K and pressure of 101.3 KPa. The reliability of the LLE experimental data was validated by the Bachman and Hand equations. The LLE data of the two systems were fitted by the activity coefficient models of nonrandom two-liquid (NRTL) and universal quasichemical (UNIQUAC), which the calculated values were in agreement with the experimental tie-line data. Meanwhile, the parameters of the two equations were also determined. Moreover, the distribution coefficients and selectivity values for the two systems were obtained from the ternary LLE data.