The present paper is designed to provide a summary of our study on the high temperature corrosion of Al2O3, SiO2 and Al2O3–SiO2 forming alloys in the gas phase and liquid phase of Na2SO4–NaCl system by comparing their corrosion resistance at 1000 °C. The obtained results show that the alumina-forming alloy experiences severe internal corrosion in the gas phase compared to in the liquid phase due to oxide cracking. This results in an increase in the inward diffusion and/or penetration of constituents of the salts and oxygen to form internal Al-oxide and Cr-sulfides. In the liquid phase, however, the formation of yttrium sulfide beneath a continuous double oxides layer of Al5Y3O12 and Al2O3 may be related to the high affinity of yttrium for sulfur. On the other hand, it is apparent from the cross-sectional observations that a SiO2 and Al2O3–SiO2 forming alloys form a continuous and dense oxides layer, and demonstrate a high resistance against internal oxidation and corrosion in both corrosive environments.