With the growing demand for high‐aluminum steel, there is an urgent need to enhance the slag resistance of magnesia‐based refractories. The wettability of high‐alumina slag on magnesia‐based refractories serves as a crucial indicator of the refractory's slag resistance. In this study, the influence of atmosphere and magnetic flux density on the wetting behavior between the slags with different basicity (CaO wt%/SiO 2 wt%) and fused magnesia is explored using a high‐temperature visualization device with a controllable static magnetic field. Compared to air and argon atmospheres, the apparent contact angle of the slag on the fused magnesia decreases significantly in a vacuum environment as the violent interfacial radical reaction. The static magnetic field of 0.5 mT can regulate the spin state of a single electron in the free radical pair, resulting in an increase of the apparent contact angle by 21.1% in a vacuum atmosphere. It provides new thoughts on the development of external field protection technology for the corrosion resistance of magnesia‐based refractories.