In this work, the discrimination between six copper alloys with archaeological interest has been carried out applying Laser Induced Breakdown Spectroscopy (LIBS) and two different chemometric methods; Principal Component Analysis (PCA) and Soft Independent Modelling of Class Analogy (SIMCA). Plasma optical emission was analyzed in the range of 200–1000 nm with an Echelle spectrometer and an ICCD camera. These copper alloys contained different amounts of Sn and other minority elements such as Pb, Al, Zn, Ni, Fe and Mn. The results show the potential applicability of the methodology in the classification of bronze alloys with a high accuracy and robustness.