The results of the influence of low-temperature plasma nitriding at 350 °C on the CrN and FeN bonds formation of Fe-Cr-Ni austenitic steel before and after nanostructure frictional treatment are presented. The measurements of high-energy resolved X-ray photoelectron Fe 2p, Cr 2p, Ni 2p and N 1s spectra and valence bands (VB) showed that chromium and iron form CrN and FeN bonds whereas the nickel is in metallic state. It is concluded that the expanded austenite formed directly on the surface of the steel after low temperature plasma nitriding can be classified as a nanocomposite medium consisting of CrN and FeN clusters dispersed in a Fe-Cr-Ni-N matrix.