This study investigated the effect of the CaO/SiO2 mass ratio of steel slag on the corrosion behavior of spinel-forming alumina-based castables with a content of MgO (3–7 wt.%). Equiweight mixtures of castables and slags were calculated by FactSage, observed by HMTA, fired at 1350 °C, and investigated by XRD. From these results, we conclude that the presence of SiO2-rich phases accelerates the growth of the liquid phase in a narrow temperature range for the tested samples, which accelerates the degradation of castables. The static corrosion test was conducted by means of the coating method at 1450 °C. The corrosion index (IC) in the regions of castables affected by slags was calculated. Phases and phase distributions were evaluated by SEM-EDS. From these results, we conclude that for the slag with the lowest mass ratio of CaO/SiO2 (1.1), the reaction zone occurs only below the slag-refractory interface, which indicates the aggressive character of this slag.