Gaseous HCl released during combustion is one reason for the severe materials degradation often encountered in power generation from waste and biomass. In this study, three stainless steels (the low alloyed EN 1.4982, the standard EN 1.4301 and the higher alloyed EN 1.4845) were tested by repeated thermal cycling in an environment comprising N 2-10%O 2-5%H 2O-0.05%HCl at both 400 and 700 °C. The materials were exposed with ground surfaces and preoxidised at 400 or 700 °C. A positive effect of preoxidation is evident when alloys are exposed at 400 °C. Oxide layers formed during preoxidation effectively suppress chlorine ingress for all three materials, while chlorine accumulation at the metal/oxide interface is detected for surface ground specimens. The positive effect of preoxidation is lost at 700 °C and corrosion resistance is dependent on alloying level. At 700 °C metal chloride evaporation contributes significantly to the material degradation. Based on the results, high temperature corrosion in chlorinating environments is discussed in general terms. © 2010 Springer Science+Business Media, LLC.