The physical properties, including flow value, apparent porosity, and mechanical strength, increased significantly with submicron spinel contents in this study. The excellent physical properties can be attributed to the close-packed microstructure and high bonding strength between spinel and aggregates/matrix. Additionally, the submicron spinel powders promoted the formation of tabular CA(6) grains that generated a cross-linked structure and enhanced the mechanical properties. The microstructures of corroded castables suggested that submicron spinel powders contributed to the formation of a continuous and thick spinel layer at the slag-refractory interface and subsequently improved the slag resistance of the castables.