Development of a new generation of multilayer coatings as well as a microstructure understanding of the mechanisms operating at the smallest length scale (nano- and atomic-scale) during wear, opens an avenue for the fabrication of future high-tech functional surfaces. Coatings for the presented work were fabricated by a pulsed laser deposition supported by magnetron sputtering. Microstructure characterization has been performed on as-deposited coatings as well as on coatings after mechanical wear test. Thin foils for detailed TEM microstructure observation were cut directly from the mechanically deformed area, using the FIB technique. Wear mechanisms operating at the small length scale of TiN/Ti/a-C : H multilayer coatings subjected to mechanical wear was studied by means of transmission electron microscopy (TEM). Cracking of the multilayer systems propagated layer by layer. The highest stress concentration during mechanical uploading was moved through the multilayer coating by breaking only one layer at the time.