The structure, phase, and composition of scale formed on a continuously cast steel slab during reheating depend on intrinsic factors (steel chemistry, microstructure, and as-cast surface condition) and extrinsic parameters (temperature, time, composition, and velocity of combustion gas atmosphere). The scale that forms on a slab normally has several layers with differing compositions and phases and knowledge of this scale structure is important in subsequent descaling and hot rolling processing steps. Formation of multiphase scale structures on steel during high temperature oxidation in reheat furnace proceeds according to a local thermodynamic equilibrium, while thickness of layers depends on kinetic conditions (mostly by diffusion). In this study, the local thermodynamic equilibrium conditions through the scale layer were simulated using different oxygen/steel ratios, which mimicked the conditions for scale formation at the external, internal, and sublayer oxide region at metal/scale boundary. Experiments were performed in a simulated combustion atmosphere using typical industrial reheat time/temperature conditions. The phases that developed in layered scale structure were documented using SEM/EDX and Raman spectroscopy. The predicted scale compositions and phases were in good agreement with the experimental results for studies with Mn and Si-alloyed carbon steel, Cr-alloyed ferritic, and Cr, Ni-alloyed austenitic steels.