In the case of Fe–1Cr–0.2Si steel, tube furnace oxidation was carried out for 120 min and 30 min. These studies, along with the high-temperature oxidation behavior of Fe–1Cr–0.2Si steel, were examined from 700 to 1100 °C. It has been observed that with an increase in the oxidation time, the oxidation weight gain per unit area of Fe–1Cr–0.2Si steel changed from a linear to a parabolic relationship. The time was shortened when the oxidation phase was linear. When the oxidation temperature exceeded 900 °C, the value of WTransition decreased, and the oxidation rule changed. It could be considered that overall, the iron oxide structure of Fe–1Cr–0.2Si steel is divided into two layers. The formation of an outer oxide of iron is mainly caused by the outward diffusion of cation, while the inward diffusion of O ion forms the inner oxides of chromium and silicon. As the temperature increases, the thickness of the outer iron oxide gradually increases, and the thickness ratio of the inner mixed layers of chromium- and silicon-rich oxides decreases; however, the degree of enrichment of Cr and Si in the mixed layer increases. After high-temperature oxidation, Cr and Si did not form a composite oxide but were mechanically mixed in the form of FeCr2O4 and Fe2SiO4, and no significant delamination occurred.