Ancient silver coins of different historical periods going from IV cent. B. C. up to recent XIX century, coming from different Mediterranean countries have been investigated with different surface physical analyses. X-ray photoelectron spectroscopy (XPS) analysis has been performed by using electron emission induced by 1.4 keV X-rays. X-ray fluorescence (XRF) analysis has been devoted by using 30 keV electron beam. Scanning electron microscopy (SEM) has been employed to analyze the surface morphology and the X-ray map distribution by using a 30 keV microbeam. Techniques were used to investigate about the patina composition and trace elements as a function of the sample depth obtained coupling XPS to 3 keV argon ion sputtering technique. (C) 2012 Elsevier B.V. All rights reserved.