Three commercial martensitic steels have been oxidised in steam at 600 and 650 °C for times up to 10000 h. The partition of minor elements within the oxide scales has been determined. Silicon forms an additional oxide layer beneath the spinel. Chromium, molybdenum and tungsten concentrate in the spinel and manganese is present in both the spinel and magnetite. Several proposed mechanisms for steam oxidation have been examined to explain the observed effects of alloy composition. Modification of the oxide defect structure and oxidant gas penetration through microcracks were identified as the mechanisms most able to explain the influence of alloy composition.