The Daero Paulos porphyry copper prospect, in the Asmara region of the central Eritrean highlands, is part of the Nakfa tectono-stratigraphic terrane, which, along with four other major and several minor terranes that constitute the Neoproterozoic Arabian-Nubian Shield, is characterized by juvenile, intra-oceanic island-arc crust. Alteration and mineralization at Daero Paulos occupy a north-northeast-trending corridor of multiphase, rhyolitic to dacitic intrusions emplaced into mafic and intermediate volcanic and subvolcanic rocks and derivative volcaniclastic strata. New U-Pb geochronological data for the volcanic rocks in the region confirm a >860-Ma age for the Neoproterozoic (Tonian) host sequence. The porphyry copper alteration evolved from early epidote-chlorite-albite through sericite-chlorite to late quartz-sericite. Local advanced argillic alteration is the erosional remnant of the lithocap that formerly dominated the shallow parts of the Daero Paulos system. A post-mineralization, Alaskan-type pyroxenite-gabbro body intruded the porphyry copper corridor, and is interpreted as the feeder for mafic dikes along the periphery of the porphyry copper system. Re-Os ages of 881.0 +/- 5.5 and 864.2 +/- 3.6 Ma for molybdenite from veinlets at Daero Paulos constrain an early Tonian timing for porphyry copper formation during early opening of the Mozambique Ocean after Rodinian supercontinent break-up. The ages also imply a rapid transition from initial rifting to the start of subduction and consequent establishment of an intra-oceanic island arc in what is now the Nakfa terrane. The molybdenite ages show that Daero Paulos is currently the oldest dated mineralization in the Arabian-Nubian Shield, and similar to 60-200 and, possibly, similar to 250 m.yr. older than porphyry copper mineralization elsewhere in the Shield. However, volcanogenic massive sulfide (VMS) mineralization could have been forming at broadly the same time, albeit not genetically associated with Daero Paulos. Preservation of such shallowly formed Neoproterozoic mineralization is mainly attributed to burial beneath thick post-amalgamation volcano-sedimentary basinal cover, collision-generated thrust sheets, and later Phanerozoic strata. (C) 2020 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.