ASTM P91 steel (viz. 9Cr-1Mo steel) was hot-dip aluminized to form a ~70 µm thick coating, and was then corroded in N 2 /0.1%H 2 S gas for 50 h at 800 and 900 ºC, to study the effect of aluminizing on the corrosion resistance of P91 steel in highly corrosive H 2 S environments. Before corrosion, the aluminized coating consisted of an Al-rich topcoat, an Al 13 Fe 4 upper layer, and an Al 5 Fe 2 lower layer from the surface. During corrosion, Al, oxygen, and sulfur diffused inwardly, while substrate elements diffused outwardly. Impurity oxygen in the gas reacted preferentially with Al to form α-Al 2 O 3 at the surface, which increased the corrosion resistance significantly. Bare P91 steel corroded quickly, to form bi-layered, fragile, nonprotective FeS scales. The coating transformed into either a (Al 13 Fe 4 , Al 5 Fe 2 )-mixed layer, AlFe layer, AlFe 3 layer, and α-Fe(Al) layer when corroded at 800 ºC/50 h, or into a AlFe 3 layer and α-Fe(Al) layer when corroded at 900 ºC/ 50 h. Interdiffusion that occurred during corrosion increased the total coating thickness, and transformed (high Al)-Fe phases to (low Al)-Fe phases. The corrosion accompanied the formation of voids and microcracks in the coating.