The basis of modern materials science is multicomponent systems, on their basis it is possible to create various combinations of phases in structural materials with a set of specified properties. The investigated system MgO-Al2O3-FeO-TiO2 is promising for the production of periclase-spinel refractories used as lining of rotary kilns during cement clinker firing, which are highly resistant to chemical corrosion when exposed to a gas environment and cement clinker components; thermomechanical stresses. However, in the reference literature and scientific articles, no information was found on the structure of the four-component diagram of the state of the MgO-Al2O3-FeO-TiO2 system, partial elements of its structure are given only in the composition of multicomponent systems [1-3]. Thus, research to the study of the subsolidus structure of the MgO-Al2O3-FeO-TiO2 system, which is the physicochemical basis for the development of compositions of periclase-spinel refractories, is urgent.