Results of spectroscopic investigation of the historical copper and copper alloy objects covered by patina and surface contamination are reported and discussed in this work. For analysis of the surface layers (bulk material, primer/grounding, patina and atmospheric contamination) the Laser Induced Breakdown (LIBS), Raman and X-ray fluorescence (XRF) spectroscopic techniques are used. Useful data on chemical structure and composition are obtained from stratigraphic analysis performed by a stepwise layer penetration with successive laser pulses. The LIBS, XRF and Raman spectra confirm the presence of patina and contamination layers of the compositions influenced by the atmospheric environment. The elemental composition reveals in the case of the original copper substrate the presence of Cu with traces of Ag and Sb, and of impurities Fe and Pb, while objects made of copper alloys (brass) show different Zn/Cu ratios greater than 20% in all cases and admixtures of Sn and Pb. Consistent results are obtained from the elemental and Raman data indicating presence of the antlerite (Cu3(OH)4SO4), carbon and microcrystalline calcite which are ascribed to patina, surface contamination (atmospheric soot) and primer layers, respectively.