This chapter presents a synthesis of the pre-break-up plate tectonics of western Gondwana and the pre- and syn-rift magmatism in the SW South Atlantic margin (Brazil, Uruguay and Argentina) and the conjugate African continental margin (Angola, Namibia and South Africa). An updated database of the geographical locations of the primary available radiometric ages is also included in this work. A systematic analysis of the K–Ar and Ar/Ar ages from outcrops and boreholes shows a marked Mid to Late Jurassic peak in the southernmost segment of the South Atlantic, related to the emplacement of the Karoo volcanics in South Africa and in Argentina (including the Falkland Islands), and an important Early Cretaceous peak with age distributions that are related to the Gondwana break-up and formation of rift basins along the incipient continental margins. In both the southern Brazilian and Argentinian margins, as well as in the conjugate Namibian and South African margins, several igneous centres and basaltic lava flows are suggestive of the influence of mantle plumes in the Early Cretaceous, which were heralded by mafic dyke swarms in Argentina, Brazil, South Africa and Namibia.