When metal oxides are reduced by methane, the nature of the reduction mechanism depends on the relative rates of decomposition and reduction. If the decomposition rate is faster than the reduction, a build-up of carbon black results, and the thermodynamics of reduction is identical to that of traditional carbothermal reduction. If, however, the reduction of oxide is faster than the decomposition of methane, reduction takes place from a metastable state where the activity of carbon is several multiples of its equilibrium value, enabling reduced reaction temperature. The interaction of methane with oxide surfaces is thus an important property in understanding and describing oxide reduction with methane, and a key factor when evaluating the suitability of oxides for metal production using natural gas. In the present work, methane decomposition and soot formation is investigated for selected oxide surfaces, and the degree of achieved metastability is estimated in view of reduction potential.