In this paper, the boiling points of methyltrichlorosilane methylvinyldichlorosilane toluene system and of the respective three binary systems are determined at 101.3?kPa with a new type of magnetical pump ebulliometer. The VLE data of the three binary systems, are correlated with the Margules, van Laar, Wilson, and NRTL equations. The equilibrium composition of the vapor phase of three binary systems are calculated from Tpx by indirect method. Fugacity coefficients are calculated after accounting for the nonideality of the vapor phase, by using calculated virial coefficients. The model parameters of liquid activity coefficient are correlated by the least square method. The vapor pressure of the pure components are obtained by using Antoine constants from the literature. At the same time, the saturation vapor presure of methylvinyldichlorosilane is measured. The VLE data of ternary system are predicted by the Wilson equation. The calculated boiling points show good agreement with the experimental data.