This paper discusses the first geochemical characterization of obsidian fragments from the prehistoric site of Roccapalumba (Palermo, Italy). The Neolithic age of the prehistoric settlement was constrained by pottery and flint tools discovered in the same archaeological context. To define the provenance of the investigated obsidian artifacts major and trace element analyses have been carried out by using scanning electron microscopy (SEM–EDX) and inductively coupled plasma mass spectrometry (LA–ICP–MS). The comparison with literature data of the Central Mediterranean source areas, based on trace elements content and their ratios allow of constraining a provenance of the Roccapalumba obsidians from the Lipari Island. The obsidian lava flow from Gabellotto Valley is the most probable source of volcanic glass at Lipari and also the most exploited in the Mediterranean area for manufactured tools. The obtained results can contribute in reconstructing the trade/exchange and procurement relationships occurred between the prehistoric human groups inhabiting Sicily during Neolithic age.