This article presents the results of research on the structural-phase regularities and behavior of periclase-spinel refractories under high-gradient thermal loads. The findings from the analysis of structural-phase variability in the refractory samples are used to achieve the desired thermal resistance. Based on the investigation of the subsolidus structure of the MgO–FeO–Al2O3–TiO2 system, predictions were made regarding the characteristics of solid-phase exchange reactions, considering the existence of solid solutions with various types of crystal structures in specific areas of the system. This enabled the application of new principles for ensuring thermal stability in the developed periclase-spinel refractories, specifically through organizing a fragmented, micro-cracked structure by combining solid-phase exchange reactions with the establishment of mobile equilibrium upon reaching stationary-state temperatures. An additional feature is the possibility of phase invertibility of solid spinel solutions, including changes in the type of spinel structure, in particular quandilite. Physicochemical research methods confirmed the enhanced ability of the material to flexibly adapt its phase composition and microstructure to thermal loads. The feasibility of these principles for achieving the structural-phase adaptability of the material to thermal shocks was validated by electron microscopy analysis.