The electronic properties of chromia scales grown between 800°C and 900°C on chromium metal and chromia-forming ferritic stainless steels were determined using room temperature PhotoElectroChemistry (PEC) experiments and the relative importance of the n- and p-character of the scales could be assessed. According to the thermodynamic previsions of defects structures, the external part of all the scales grown in oxygen exhibits band gap energy around 3.5 eV, with a marked p-type character on chromium and a possibly n-type behaviour on stainless steels. On the contrary, the internal part of the scales is always n-type, with predominant interstitial chromium defects. A major change appears when chromium or stainless steels are oxidised in water vapour-argon mixtures, where the absence of a p‑type semiconductor in the scales could be evidenced. Hydrogen defects are thought to be responsible of this particular behaviour which leads to a strong reduction of residual stresses due to increased high temperature relaxation. Moreover, the inversion of the growth direction resulting from high mobility of the OH defects makes the chromia scales grown in water vapour more adherent than when grown in oxygen.