This study presents a comprehensive investigation of the formation, composition, and behaviour of oxide layers during the high-temperature oxidation of four different steel alloys (16Mo3, 13Cr, T24 and P91) at a uniform temperature of 650 °C. The research combines CALPHAD (CALculation of PHAse Diagrams) calculations, thermogravimetric analysis (TGA) and advanced microscopy techniques, including scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD), to elucidate the complex mechanisms controlling oxidation kinetics and oxide layer development. CALPHAD calculations were used to determine the thermodynamically stable phases for each steel type at 650 °C. The results showed different phase compositions, highlighting the importance of steel composition in the formation of oxide layers. Each steel grade exhibited different kinetics, with 16Mo3 steel showing the highest oxidation rate, followed by 13Cr, T24 and P91. This variability highlights the role of steel composition, particularly chromium content, in determining oxidation behaviour. These results have significant implications for temporary overheating in industrial applications and contribute to a deeper understanding of oxidation processes in steels.