Archaeological artefacts recovered at Castanheiro do Vento (Northern Portugal) were characterised by integrating macro and micro-energy dispersive X-ray fluorescence spectrometry (EDXRF) and scanning electron microscopy with X-ray microanalysis. The collection includes metallurgical remains (ceramic crucibles, a metallic nodule and a vitrified fragment) and metals (tools and ornaments) whose chronology spans from the Chalcolithic to the Roman Age. The study of production remains was able to identify distinct copper-based metallurgical operations including the smelting of copper ores, the melting of copper and tin and/or the melting of bronze scrap. Micro-EDXRF identified copper and arsenical copper tools as well as bronze and leaded bronze ornaments. The composition of tools (Cu with varying As contents: 0.46–3.6%) reveals an incipient technology, typical of the Chalcolithic till the Middle Bronze Age. On the contrary, ornaments are composed by different alloys – low tin bronze (4.8% Sn), high tin bronze (14.9% Sn) and high tin-leaded bronze (16.5% Sn and 2.4% Pb) evidencing technological and economic choices that clearly indicate a late period such as the Roman Age. In conclusion, this multiproxy approach was able to study those ancient artefacts with a minimum impact on their archaeological and museological significance while providing important answers to the interpretation of the archaeological settlement and to better understand the metallurgical evolution in the Portuguese territory.