This contribution describes, through letters and printed documents, the history of the Catalogo di antiche medaglie consolari e di famiglie romane (Naples, 1855) by the collector Gennaro Riccio, the connections with the training environment, the scientific choices and the printing techniques of the book. The illustrated plates of ancient coins were produced experimentally in relief with the galvanoplastic method and with a special metal hue simulating gold, silver and bronze, in order to obtain a very realistic view of these coins. This method of illustration was successful, but also suffered criticism; it gained fame and later it was forgotten. The spectroscopic investigations carried out on some papers for the identification of the material sand of the execution techniques (ft-ir, Raman and frx spectra) enable the reconstruction of the kind of paper used for the hollow printing, the layer of «white lead» and the composition of metal used in hues suggesting the presence of gold, silver and copper coins in relief, but reveal the absence of precious metals and especially the presence of copper particles (for gold and bronze coins) and tin (for silver coins).