The origin of intraplate carbonatitic to alkaline volcanism in Africa is controversial. A tectonic control, i.e., decompression melting associated with far-field stress, is suggested by correlation with lithospheric sutures, repeated magmatic cycles in the same areas over several million years, synchronicity across the plate, and lack of clear age progression patterns. Conversely, a dominant role for mantle convection is supported by the coincidence of Cenozoic volcanism with regions of lithospheric uplift, positive free-air gravity anomalies, and slow seismic velocities. To improve constraints on the genesis of African volcanism, here we report the first radiometric and isotopic results for the Catanda complex, which hosts the only extrusive carbonatites in Angola. Apatite (U-Th-Sm)/He and phlogopite 40Ar/39Ar ages of Catanda aillikite lavas indicate eruption at ca. 500–800 ka, more than 100 m.y. after emplacement of abundant kimberlites and carbonatites in this region. The lavas share similar high-μ (HIMU)–like Sr-Nd-Pb-Hf isotope compositions with other young mantle-derived volcanics from Africa (e.g., Northern Kenya Rift; Cameroon Line). The position of the Catanda complex in the Lucapa corridor, a long-lived extensional structure, suggests a possible tectonic control for the volcanism. The complex is also located on the Bié Dome, a broad region of fast Pleistocene uplift attributed to mantle upwelling. Seismic tomography models indicate convection of deep hot material beneath regions of active volcanism in Africa, including a large area encompassing Angola and northern Namibia. This is strong evidence that intraplate late Cenozoic volcanism, including the Catanda complex, resulted from the interplay between mantle convection and preexisting lithospheric heterogeneities.