Binary and ternary transition metal nitrides coatings have been used in numerous applications to increase the hardness and improve the wear and corrosion resistance of structural materials, as well as in various high-tech areas, where their functional rather than tribological and mechanical properties are of prime importance (Munz, 1986; Chen & Duh, 1991; PalDey & Deevi, 2003; Ipaz et al., 2010). Up to now, Ti-Al-N and Cr-Al-N films have been synthesized by a variety of deposition techniques including cathodic arc evaporation (Cheng et al., 2001), ion plating (Setsuhara et al., 1997), chemical vapor deposition (CVD) or plasma-enhanced CVD (Shieh & Hon, 2001) and d.c. / r.f. reactive magnetron sputtering (Musil & Hruby, 2000; Sanchez et al., 2010). Performance of these coatings is equally dependent on their chemical composition and long-range crystalline structure, as well as on the nature and amount of impurities and intergranular interactions. Significant improvement in the mechanical properties has recently been achieved with multicomponent superlattice, multilayers and nanocomposite nitride coatings. In the case of such multilayers systems, not only is close control of the elemental composition (stoichiometry) and modulation period necessary to optimize the properties of the coatings, but the influence of chemical bond formation between the components is also of prime importance. Therefore, it is necessary to take special care when the conditions of preparation are nonequilibrium, activation of CVD and PVD by plasmas or energetic particle beams are applied, occasionally leading to unpredicted deviations, both in composition and structure. As is highlighted in this study, nitride coatings or nitrided surfaces based in Chromium and Aluminium materials can be analyzed in detail by X-ray photoelectron spectroscopy (XPS) due to its excellent element selectivity, quantitative character and high surface sensitivity. More importantly, XPS reflects the atomic scale chemical interactions, i.e. the bonds between neighboring atoms Cr-N, Al-N, Ti-N, Ti-Al-N and thus it also provides reliable structural characteristics for amorphous or nano-crystalline coatings of complex composition, for which application of diffraction techniques is not straightforward.