Knudsen effusion mass spectrometry was used to study vaporization processes and thermodynamic properties of twenty samples of chromium-containing slags in the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 system in the temperature range 1850–2750K. Tungsten cells were used and Cr2O3 solid was used as a reference material. The system was calibrated using liquid gold. As FeO was the first emanating vapor species, monitoring of the chromium-containing species could be carried out only after the complete vaporization of FeO. This, however, was found to have very little impact on the concentration of the slags investigated. During the measurements, the ion current intensities of CrOR and CrOR2 species in the mass spectra of the vapor over the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 samples were monitored and compared with those corresponding to solid Cr2O3. Data on the partial pressures of vapor species as well as the activities of Cr2O3 as a function of temperature were obtained. The results are expected to be valuable in the optimization o