Corrosion of Fe‐6Si steel during heat treatment at 500 and 700 °C in air, argon, and vacuum was studied. Phase and structure analysis were carried out using Mössbauer spectroscopy, X‐ray diffraction, scanning electron microscopy, Glow discharge optical emission spectrometry, and X‐ray photoelectron spectroscopy. Measurement of magnetic hysteresis loops were used to follow changes in magnetic properties. Structure and phase composition of surface layers change in dependence on annealing conditions. Besides the content of hematite, magnetite, and fayalite an increase in silicon content at the surface was detected namely after annealing at 700 °C. Our results show that good magnetic properties of the studied Fe‐6 wt% Si steel are not deteriorated substantially by annealing at 500 and 700 °C in air, argon, and vacuum. Therefore this steel can be applied in magnetic circuits working at high temperatures.