Protective, chromate substitute thin layers on roughened galvanized surfaces produced at OCAS (Arcelor, Belgium) were characterized and compared using Scanning Electron Microscopy (SEM+EDS), Atomic Force Microscopy (AFM), Nanoindentation and X-ray Photoemission Spectroscopy (XPS). EDX maps, line scans and point analyses obtained at various places of the surfaces have shown differences between the CVD and silane nanolayers in the matter of thickness distribution and composition. At cross-section specimens the thickness of the layers could be shown. The hardness differences caused by layer thickness variations are hard to follow by nanoindentation as the penetration depth of the indenter is much larger than the thickness of the coatings. XPS measurements can distinguish between the chemical states of silicon in CVD and silane coatings.