Abstract: size of spinel crystals in the CaO-SiO₂-MgO-Al₂O₃-Cr₂O₃ system was investigated using lab experiments carried out in a carbon tube furnace. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD) were used to analyze the microstructure, components, and the mineral phases of synthetic slags. FactSage 7.1 was used to calculate the crystallization process of the molten slag. The results showed that the addition of Fe₂O₃ promoted the precipitation of spinel crystals and inhibited the formation of dicalcium silicate. The size of spinel crystals increased from 2.74 to 8.10 μm and the contents of chromium and iron in the spinel varied as the Fe₂O₃ addition was increased from 0 to 20wt%. Fe₂O₃ thermodynamically provided the spinel-forming components to enhance the formation of FeCr₂O₄, MgFe₂O₄, and Fe₃O₄. The addition of Fe₂O₃ increased the fraction of liquid phase in a certain temperature range and promoted diffusion by decreasing the slag's viscosity. Therefore, Fe₂O₃ is beneficial to the growth of spinel crystals in stainless steel slag.