We consider two amorphous multilayer nanostructures (MLNS) [(Co 45 Fe 45 Zr 10 )/a-Si: H] 41 -I and [(Co 45 Fe 45 Zr 10 ) 35 (Al 2 O 3 ) 65 /a-Si:H] 41 -II that were obtained by ion-beam sputtering. For determination of the phase composition of the buried amorphous silicon interlayers in these MLNS, we used nondestructive ultrasoft X-ray emission spectroscopy technique (USXES). The use of the USXES enables to register the silicon Si L 2,3 -spectra providing the information about the local partial densities of Si s and d occupied states of silicon valence band in silicon-contained materials. According to the simulation and fitting procedure to the experimental data, Fe 3 Si and a small amount of oxide (SiO 2 :H) were found in the interlayer of MLNS-I. At the same time, the content of silicon dioxides (SiO 2 ) decrease from surface layers to the deep ones. On the other hand, simulation of the phase composition of MLNS-II reveals the presence of the silicides Fe 3 Si and Co 2 Si, oxides SiO 2 and SiO 1.3 , and a small amount of a-Si:H. The percentage of cobalt silicide Co 2 Si and suboxide SiO 1.3 increased in the deep layers of the MLNS-II. KEYWORDS interfaces, ion-beam sputtering, multilayer nanostructures, silicides of 3d metals, silicon oxides, ultrasoft X-ray emission spectroscopy