The corrosion and vaporization behavior of eight commercial refractories containing Cr2O3 were investigated under simulated pressurized pulverized coal combustion (PPCC) conditions at 1723 K in the presence of liquid slag. The corrosion resistance of the refractory materials decreased with increased content of free Cr2O3, because bursting (reaction of Fe3O4 with Cr2O3) occurred. Refractories containing MgCr2O4 with dissolved Al2O3 showed the highest corrosion resistance, Thermodynamic calculations showed that CrO3 and CrO2(OH)(2) were the most volatile species in air and in PPCC flue gas, whereas additions of A(2)O (A = Na and K, minor slag component) increased the chromium vaporization significantly because of A(2)CrO(4) formation. Knudsen effusion mass spectrometry measurements showed that the chromium vaporization of refractories was directly correlated to the Cr2O3 content of the material. In contrast, refractories containing MgCr2O4 shelved a significant decrease in chromium vaporization.