This study investigates the comparison of the Raman signatures of different phases used in underglaze, inglaze and overglaze decors of selected European, Chinese and Japanese porcelains and enameled metalworks, which are particularly representative of technological developments in enameling. Specifically, the article deals with the main structural types or host networks (corundum/hematite, spinels, zircon, cassiterite, pyrochlore, apatite, sphene, etc.) used for colored enamels on porcelain, earthenware or metal rather than considering all types of pigments and opacifiers. According to the results, Raman microspectroscopy allows identifying of the fingerprint spectra of milestone technologies and represents a simple and rapid tool for detecting copies. Particular attention is paid to the information deduced from the examination of the associated ‘background’ and signatures from electronic transitions induced by uncontrolled traces or voluntary addition of rare earths (luminescence). The relationship between the grinding procedure and Raman signature is also discussed.