Over the centuries, humans have developed different systems to protect surfaces from the influence of environmental factors. Protective paints are the most used ones. They have undergone considerable development over the years, especially at the turn of the 19th and 20th centuries. Indeed, between the two centuries, new binders and pigments have been introduced in the constituent materials of paints. The years in which these compounds have been introduced and spread in the paint market allow them to be defined as markers for the dating of paints and painted artifacts. The present work is focused on the study of the paints of two vehicles of the Frankfurt Museum of Communication, i.e., a carriage and a cart, that was designed for the German Postal and Telecommunications Service roughly between 1880 and 1920. The characterization of the paints was performed through in situ non-invasive techniques, i.e., portable optical microscopy and multispectral imaging, and laboratory non-destructive techniques, i.e., FT-IR ATR spectroscopy and SEM-EDS. The analytical investigation and the comparison with the data reported in the literature allowed us to determine the historicity of the paints, which are all dated before the 1950s.