Vapor-liquid equilibrium (VLE) data for the strongly associated ternary system methanol + water + ethanoic acid and the three constituent binary systems have been determined by the total pressure-temperature-liquid-phase composition-molar excess enthalpy of mixing of the liquid phase (p,
T,
x, HmE) for the binary systems using a novel pump ebulliometer at 101.325 kPa. The vapor-phase compositions of these binary systems had been calculated from Tpx and HmE based on the Q function of molar excess Gibbs energy through an indirect method. Moreover, the experimental T, x data are used to estimate nonrandom two-liquid (NRTL), Wilson, Margules, and van Laar model parameters, and these parameters in turn are used to calculate vapor-phase compositions. The activity coefficients of the solution were correlated with NRTL, Wilson, Margules, and van Laar models through fitting by least-squares method. The VLE data of the ternary system were well predicted from these binary interaction parameters of NRTL, Wilson, Margules, and van Laar model parameters without any additional adjustment to build the thermodynamic model of VLE for the ternary system and obtain the vapor-phase compositions and the calculated bubble points.