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This paper presents a metallographic analysis of copper artifacts from an extraordinary Polish cemetery of Lublin–Volhynian culture dated 4000–3800 BC (Wilk in Analecta Archaeologica Ressoviensia, 2014, pp. 209–243). The Książnice necropolis, Busko-Zdrój county located in South Poland, is characterized by an unprecedented collection of prestigious objects made of copper, rare in the Eneolithic period in Poland. The archaeological studies supplemented with materials analyses give knowledge of prehistoric metallurgy and the processing of copper. For the described group of artifacts, non-destructive microscopic studies were performed including chemical analysis by means of X-ray fluorescence and energy-dispersive X-ray spectroscopy using a scanning electron microscope. The mentioned studies allowed for raw material characteristics of this important discovery.