We report on the archaeometallurgical analysis of eight pieces of copper recovered from the Villa JMC-1 cemetery (Pitren Complex, Early Ceramic period) in the locality of Labranza, La Araucania. These artifacts provide the earliest evidence of metal use in southern Chile. They are also the southernmost prehispanic metal artifacts ever found in South America. These contextualized results complement those obtained from the analysis of an earring from Kilómetro 0—Enlace Temuco (El Vergel Complex, Late Ceramic period), an archaeological residential site dated to almost 500 years after the Labranza cemetery. Particle Induced X-ray Emission, X-ray radiography, and stereomicroscopy analyses allow us to offer an elemental characterization of the pieces, an assessment of their manufacturing process, and a comparison between the metals and alloys discovered. We follow with a discussion of proposals regarding cultural relations in the Araucania region during different time periods.