New composite material-multi-walled carbon nanotubes (MWCNTs) coated with thin iron films-have been prepared by MOCVD growth technique using iron pentacarbonyl as the iron source. Their structures and morphologies were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and thermal gravimetric analysis. The NEXAFS C1s-and Fe2p-spectra of the composite materials MWCNTs-pyrolytic Fe were studied by total electron yield mode with using synchrotron radiation Russian-Germany beamline at BESSY-II. The study has shown that top layers of the MWCNTs in composite do not have essential destruction, coating of MWCNT's-surface is Fe3O4 and this coating is continuous. The iron oxide adhesion is provided by chemical binding between the carbon atoms of the MWCNT's top layer and the oxygen atoms of the coating.