Cr 25.2 Al 19.5 Si 4.7 N 50.5 thin films were deposited on steel substrates by cathodic arc plasma deposition. They consisted of alternating fcc-Cr(Al)N/hcp-Al(Cr,Si)N nanolayers. They were corroded at 900 and 1000 o C for 5-100 h in N 2 /0.1%H 2 S gas atmosphere. Their corrosion mechanism, the structure of the formed scales, and the role of film-constituting elements during corrosion were studied. Despite the presence of hydrogen and sulfur in the corrosion gas, the films displayed good corrosion resistance because Cr, Al, Fe preferentially reacted with impurity oxygen in the corrosion gas to form Cr 2 O 3 , Fe 3 O 4 , and amorphous Al 2 O 3 owing to the thermodynamic stability of these oxides. The films were corroded by the outward diffusion of Cr, Al, Fe and nitrogen as well as the inward transport of sulfur and then oxygen. Silicon in the film was primarily oxidized by the inwardly transported oxygen. This study aimed to investigate the high-temperature corrosion behavior of nano-multilayered Cr 25.2 Al 19.5 Si 4.7 N 50.5 thin films in a serious H 2 S-containing environment.