The last decade has seen significant advancement in the geochemical fingerprinting of obsidian sources and obsidian artifacts on both sides of the Red Sea Rift. Despite the presence of large numbers of obsidian-rich volcanoes, this region‘s sources are poorly known, and their exploitation by human groups minimally researched. Recent focused archaeological investigations on the prehistory of south Arabia and the African Hornhave demonstrated the importance of this region for hominin dispersals, and for the forging of early human contact and interaction networks which accompanied major societal transformations such as Neolithization. This paper presents an overview of the results of obsidian sampling and sourcing carried out by the VAPOR program and its collaborators, and provides a first look at the way such results enable us to reconstitute inter-Arabian, Afro-Arabian, and inter-African human mobility and interaction and their relationship to the Neolithization of the region.