This paper deals with the investigation of complex-alloyed nickel aluminides obtained from oxide compounds by aluminothermic reduction. The aim of the work was to study and develop the physicochemical basis for obtaining complex-alloyed nickel aluminides and their application for enhancing the properties of coatings made by electrospark deposition (ESD) on steel castings, as well as their use as grain refiners for tin bronze. The peculiarities of microstructure formation of master alloys based on the Al-TM (transition metal) system were studied using optical, electronic scanning microscopy and X-ray spectral microanalysis. There were regularities found in the formation of structural components of aluminum alloys (