Corrosion behaviours of Fe–25Cr, Fe–25Cr–2Mn–1Si, Fe–25Cr–20Ni, 310SS, Ni–25Cr, and Ni–25Cr–2Mn–1Si (all in wt%) with and without NaCl–KCl deposits in Ar–60%CO2–20%H2O gas at 750 °C were studied. Without salt deposits, Fe–25Cr performed protectively, while Fe–25Cr–20Ni and Ni–25Cr underwent breakaway oxidation with multilayered scales formed. Adding alloy elements Si + Mn increased the corrosion resistance of all alloys by forming additional Mn-rich oxides and silica. Surface deposits of NaCl–KCl accelerated corrosion, forming porous Fe-rich oxide nodules for Fe–25Cr and thick, porous scales and internal oxidation zones for all other alloys. The protective effect of Si + Mn alloying disappeared in the presence of chlorides. Limited intergranular carbides were observed for all alloys in the gas-only condition. The extent of carburisation increased with the presence of chloride deposits for all Fe-based alloys, but remained unchanged for Ni-based alloys. Corrosion of these alloys at 750 °C is compared with that at 650 °C. The effect of chlorides in volatilising metals at 750 °C is discussed.