The oxidation of three Fe-xSi alloys (x = 5, 9, 13 at.%) under 10−20 atm O2 at 800 °C formed in all cases SiO2 layers. For Fe-5Si this layer broke down and healed up periodically forming an anomalous internal oxidation zone with spherical and net-shaped SiO2 particles. The SiO2 layer formed on the other two alloys spalled off due to the growth and thermal stress accumulated. The critical silicon content needed for its external oxidation on Fe-Si alloys calculated according to an extension of Wagner's theory under the present experimental conditions is significantly smaller than the experimental results.