The surface of hot stamping steel is severely oxidized during heating, holding, and transfer from the heating furnace to the stamping die in the production of traditional automotive parts. Coating-free hot stamping steel with Cr and Si elements exhibits excellent oxidation resistance during hot stamping without the protection of a surface coating. This paper investigates the oxidation behavior of three types of hot stamping steel at 800–1200 °C. The results show that although Cr-Si hot stamping steel performs excellently short-term (≤7.5 min) for oxidation resistance, its long-term (≥15 min) or high-temperature (≥1100 °C) oxidation resistance is much lower than that of the conventional hot stamping steel 22MnB5, affecting the production and surface quality control of the new coating-free Cr-Si hot stamping steel. By analyzing the oxidation kinetics and characterizing the structure of oxide layers in hot stamping steel, it was found that the structural change in the Cr and Si element enrichment layer between the oxide scale and the substrate varied in oxidation performance at different temperatures. When the oxidation temperature was below 1000 °C, the solid Cr and Si enrichment layer acted as a barrier to prevent the diffusion of Fe ions. When the oxidation temperature exceeded 1100 °C, the molten Cr and Si enrichment layer effectively adapted to the substrate and avoided blistering. Meanwhile, Fe₂SiO₄ penetrated the Fe oxide layer along the grain boundary and became a rapidly diffusing channel of Fe ions, contributing to a significant increase in the oxidation rate.