Conversion-electron Mössbauer spectroscopy analysis of model electrochemical cells, comprising porous 57Fe-enriched (La0.9Sr0.1)0.98Cr0.6Fe0.3Mg0.1O3−δ electrodes and lanthanum gallate solid electrolyte, showed no reductive decomposition of the perovskite electrode material in H2-containing atmosphere at 1073K, even in the steam electrolysis regime. The predominant state of iron cations in the electrode surface layers was found to remain trivalent irrespective of the oxygen partial pressure in surrounding atmosphere and polarization, whilst oxygen coordination of Fe3+ decreases on lowering electrode potential.