Three types of alloys were recognized when analyzing pre-Columbian artifacts from the North of Peru: gold, silver, and copper alloys; gilded copper and silver; silvered copper; tumbaga, i.e., copper or silver enriched on gold at the surface by depletion gilding. In this paper, a method is described to differentiate gold alloys from gilded copper and from copper-gold tumbaga, and silver alloys from silvered copper and copper-silver tumbaga. This method is based on the use of energy-dispersive X-ray fluorescence, i.e., on a sophisticated analysis of XRF-spectra carrying out an accurate determination of Cu(K α /K β ), Ag(K α /K β ), Au(L α /L β ), and Au-L α /Cu-K α or Ag-K α /Cu-K α ratios. That implies a dedicated software for the quantitative determination of the area of X-ray peaks. This method was first checked by a relevant number of standard samples and then it was applied to pre-Columbian alloys from the North of Peru. © 2013 Springer-Verlag Berlin Heidelberg.