An amorphous metal alloy of the FeCrB system was studied during the crystallization by thermal annealing. Such an alloy is a perspective candidate for the role of an intermediate layer in multilayer covering for cutting tools. By the using of the thermoelectric voltage measurement, positron annihilation spectroscopy, and X-ray photoelectron spectroscopy, the conjoint research was performed for the study of the conduction and delectron band state in the amorphous metallic alloy FeCr 15 B 15 , which intersects each other by the energy. The results of all the studies agree with each other and indicate the change in the effective charge of the d-shell by 1 electron during crystallization.