The specific features of changes in the electronic structure of multi-walled carbon nanotubes (MWCNTs) due to the interaction with an amorphous tin oxide in the SnO_x/MWCNT composite formed by magnetron sputtering have been investigated using X-ray spectroscopy. It has been shown that the formation of chemical bonds responsible for significant changes in the local and electronic structures of the outer layers of MWCNTs occurs at the boundaries of the “amorphous oxide/MWCNT” contacts. The vacuum annealing of the composite leads to the disturbance of the chemical interaction at interfaces of the composite and to a partial recovery of the local structure of the outer layers of MWCNTs. A decrease in the amount of oxygen in the tin oxide under vacuum annealing conditions causes an increase in the number of unpaired Sn 5s electrons, which, in turn, enhances the charge transfer through the interfaces in the composite and leads to a splitting of the π^*-subsystem of the outer layers of MWCNTs.