The Guadalquivir River Valley constitutes the main geographic environment for the earliest development of political structures in the South of the Iberian Peninsula. The inception of Cu-metallurgy over the millennia 4th to 2nd BC in this region coincides with the rise of social complexity as well as the strategic control of the territory based on the command of the supply of mineral resources. One of the main tools in the study of metallurgical processes and goods movement is the analysis of metal provenance by means of Pb isotope composition. This study includes 98 new Pb isotope analyses performed on Cu mineralizations, many of them with archaeological evidence of exploitation by the first metallurgical societies. The results provided here represent a substantial complement to those presented in published databases and allow for a better discrimination of potential sources for raw material supply of minerals used in the metallurgical processes. The existence of uncertainties introduced by the overlapping of Pb-isotope signatures of Cu-ores obtained from different geological contexts and presence of radiogenic Pb in a number of samples is pointed out.