Abstract: In order to provide basic data for study of the separation of ethylenediamine (EDA)−silane coupling agent N−β− (Aminoethyl)−γ−aminopropyltrimethoxysilane (KH792) mixture by distillation process, the saturated vapor pressure of silane coupling agent KH792 at 3−12 kPa and the vapor−liquid equilibria (VLE) data of binary system of EDA−KH792 at 8 kPa were determined using Rose vapor–liquid equilibrium reactor, respectively. The reliability of the measured data was verified by Herington area integral method. On this basis, NRTL and Wilson activity coefficient models were used to correlate and simulate the experimental data. The results show that the average deviation of vapor phase composition in EDA−KH792 system associated with NRTL and Wilson models is 0.005 5 and 0.007 9, respectively. The average deviation of equilibrium temperature is 0.897 1 and 1.163 1 K, respectively. The deviation of the correlation data between the two models is small, and the accuracy of the correlation is high, which can be used for the calculation of vapor–liquid equilibrium in this system. However, NRTL model has a smaller deviation and higher accuracy in data association, making it more suitable for vapor–liquid equilibrium calculations in this system.