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Abstract: The Red Sea and surrounding area formed through dynamic uplift and rifting of Afro-Arabia, and associated volcanism (both oceanic and continental in character). As a result, volcanic landforms and products are widespread and play a vital role in the natural and cultural landscapes of humans occupying the highlands and lowlands on both sides of the Red Sea. Archaeologists have suggested for some time that Afro-Arabian trade in obsidian had its roots in the prehistoric period and that the region was very likely the source of an abundance of obsidian artefacts found as far afield as Egypt, the Persian Gulf and Mesopotamia, and which do not match the well-known Anatolian, Transcaucasian or Mediterranean sources. Nonetheless, the southern Red Sea is one of the few obsidian-rich regions exploited in antiquity that has been barely investigated. In this paper, we highlight new geochemical analyses (carried out by LA-ICP-MS) of obsidian sources in Southern Arabia and beyond, that enhance our knowledge of obsidian exploitation from as early as the Neolithic period, and which enable us to evaluate the role that highland Yemen obsidian sources played in prehistoric long-distance trade. In addition, we present new evidence for explosive volcanic eruptions that likely affected the highland populations of Yemen in the 4th millennium BC. [Copyright &y& Elsevier]