In this article, a brief review of the development of the Knudsen effusion mass spectrometric (KEMS) approach in the Theoretical Metallurgy Department of the KTH Royal Institute of Technology and in the in the Laboratory of Metallurgy of the Helsinki University of Technology and modifications of quadrupole model QMG420 mass spectrometers, is presented. The thermodynamic data obtained from vaporization of standards, such as NaCl, CsCl, B2O3, and Ag, and of the B2O3–Al2O3 and ZnO–P2O5 systems is compared with the data obtained using a magnetic MS1301 mass spectrometer. For the first time, composition of the vapor phase over the Dy2O3–DyF3, CaO–CaCl2, and Cu–Mg systems and the partial pressures of components at high temperatures are investigated. The experimental data obtained for the investigated systems are used for prediction of the vaporization processes and modeling of thermodynamic properties and high-temperature phase equilibria in the multicomponent systems used in metallurgy. An account is given of the detailed studies of the vaporization processes and thermodynamic properties of some multicomponent systems composed of oxides, fluorides, and carbonates forming mold powders for continuous casting of steel. Some new directions of the ongoing studies by the KEMS method are summarized.