Steel is one of the most important materials and finds its applications almost everywhere around us. Nevertheless, despite its excellent properties, steel is prone to a degradation process corrosion. Although corrosion cannot be stopped completely, its negative effects can be minimized by means of zinc coatings. Diverse zinc coatings were invented several decades ago, however, due to numerous open issues regarding to their structure and properties as well as continuously increasing demands for better corrosion protection, they are still under intensive research and development. In this context, two kinds of advanced coating systems are considered: binary Zn-Cr and ternary Zn-Mg-Al alloyed coatings. Both coatings were investigated by surface sensitive methods, namely X-ray photoelectron spectroscopy and Auger electron spectroscopy. While Zn-Cr coatings were analyzed with respect to their elemental and chemical composition, the study of Zn-Mg-Al coatings focused also on the initial stages of corrosion induced by short exposures to NaCl rich environments. Within the experimental part of the here presented work, several issues and problems appeared and had to be solved, e.g. the evaluation routine for XPS data or different degradation processes connected to standard measurements or to Ar+ ion sputtering. Nevertheless, on the basis of the gained knowledge and understanding of the methods as well as of the material systems, the assigned scientific and analytical tasks could be successfully fulfilled and are reported in numerous scientific publications constituting the present thesis which is written in a cumulative form.