<p>In view of application limitation of calcium hexaaluminate in metallurgical smelting caused by poor sintering densification, achieving the modification of the calcium hexaaluminate is highly expected. Therefore, this work explored the effect of La₂Ce₂O₇ on the sintering densification, wetting behavior and corrosion resistance of the CA₆ materials, aiming to achieve the optimization design of the CA₆ materials. The research showed the La₂Ce₂O₇ was incorporated into the CA₆ grains, where the introduced Ce⁴⁺ would substitute Al³⁺ in the spinel block and the La³⁺ would substitute Ca²⁺ in the mirror layers accompanied by the formation of cation vacancy defects. Such behavior greatly supported the CA₆ grains to grew along the direction perpendicular to the basal plane and was responsible for a more equiaxed morphology and highly dense microstructure with improved mechanical properties and thermal shock resistance. Moreover, reduction of apparent porosity and improvement of wettability inhibit the penetration and adhesion of molten steel on the material surface, thus achieving the improvement in corrosion resistance of molten steel. Consequently, the introduction of La₂Ce₂O₇ is expected to design the CA₆ materials with improved sintering densification, wetting behavior and corrosion resistance, promoting its better application for prospective metallurgical smelting.</p>