To provide an accurate prediction of the product component dependence of temperature and pressure in vacuum distillation and give convenient and efficient guidance for the designing of the process parameters of industrial production, according to the molecular interaction volume model (MIVM), the separation coefficient (β) and vapor-liquid equilibrium composition of Au-Ag alloy at different temperatures are calculated. Combined with the vapor-liquid equilibrium (VLE) theory, the VLE phase diagrams, including the temperature-composition (T-x) and pressure-composition (p-x) diagrams of Au-Ag alloy in vacuum distillation are plotted. The triple points and condensation temperatures of gold and silver vapors are calculated as well. The results show that the β decreases and the contents of gold in vapor phase increase with the distillation temperature increasing. Low pressures have positive effect on the separation of Ag and Au. The difference between the condensation temperatures of gold and silver is about 450 K in the pressure range of 1-10 Pa.