Following earlier research which has shown that Al2O3 scales are more effective than Cr2O3 scales in protecting iron-nickel-base alloys against sulphur-containing gases, several commercial steels, 310 stainless, 314 stainless, and 321 stainless, and an experimental ferritic steel, FeCrAlHf, have been pack aluminized to develop aluminide coatings for applications in mixed-gas environments of high sulphur and low oxygen potential. Results are presented for long-term exposures to H2/1.6% H2O/1.1% H2S at H2S at 750°C and 1000°C under thermal-cycling conditions. Short-term tests in this environment at 750° C led to considerable sulphidation of the uncoated, Cr2O3-forming alloys. The aluminized alloys were much more resistant to sulphidation than the uncoated materials, with relatively little degradation being observed after 200 hr at 750°C. Even at 1000°C, with the exception of the ferritic steel, the coated systems showed reasonable degradation resistance for 500 hr. Eventual sulphidation resulted from back diffusion of aluminum into the substrate and dilution of the coating surface in this element until an Al2O3 scale was unable to reform and base metal sulphides could develop. The composition of the substrate was important in determining the rate of aluminium depletion from the coating, with interdiffusion being faster in ferrite-rich matrices than the austenite matrices. Thus, the higher nickel-containing alloys developed the most effective coating systems for use in such environments. The structures of the various aluminized systems are presented and their mechanisms of protection and breakdown are discussed and correlated with their performances under these high-temperature conditions.