Thin films play an important role in electron microscopy as they can be used to improve the contrast and stability of specimens, as well as to make specimens electrically conductive. In order to avoid overlapping of specimen and coating structures, it is necessary to understand how thin films are formed in the various coating technologies and how to create them reproducibly as part of the different preparation techniques for electron microscopy. In contrast, electron microscopy can be applied to learn more about the structural details of thin films used, for instance, in the optical coating industry. Heat shock fracturing and Pt-C surface replication of the cross sections resulted in reliable transmission electron micrographs (TEM) of the coating microstructure. These studies demonstrate that, under optimal conditions, it is possible to find a correlation between the measured optical properties and the microstructure of the coatings. TEM replica investigations reveal single events, so they can be useful if discrepancies in the (statistical) physical data have to be investigated.