A CaO-MgO-Al₂O₃-SiO₂ glass–ceramic coating was prepared by the slurry method and subsequent sintering to improve the corrosion resistance of 316L steel in liquid lead–bismuth eutectic alloy at high temperatures. The glass–ceramic coating, sintered at 884 °C, was dense and demonstrated strong adhesion to the substrate. It was composed of the crystalline phases diopside (CaMgSi₂O₆) and anorthite (CaAl₂Si₂O₈) and had an average Vickers hardness of 595 HV, which was over three times that of 316L steel. After corrosion in an oxygen-saturated, static lead–bismuth eutectic alloy at 500 °C for 1000 h, the uncoated 316L experienced significant mass gain (0.04 g) due to severe oxidative corrosion, resulting in the formation of Fe₃O₄ and Pb₂O on its surface. In contrast, the glass–ceramic-coated specimens showed a very small mass gain (0.0012 g) after corrosion. The coating maintained good thermal stability; its crystalline phase composition remained largely unchanged after the corrosion test. The glass–ceramic coating still exhibited dense microstructure and tightly adhered to the substrate after corrosion. There was no evident penetration of lead–bismuth into the coating, and no dissolution of the coating’s elements into the lead–bismuth alloy was detected. These observations confirm that the glass–ceramic coating possessed superior corrosion resistance in liquid lead–bismuth eutectic environments.