We use offshore 2-3D seismic reflection and potential field data coupled with field work to investigate the control of lithospheric heterogeneity and shear zone rejuvenation on the mode of extension and the architectural segmentation of the southern Angola margins. The pre-rift basement is inherited from several Precambrian deformation events ended by the Pan-African/Brasiliano orogen that accreted four different age-dependent lithospheric domains with contrasted thickness, fabrics, thermal structure, and chemical composition. From north to south, the continental crust is composed of Neoproterozoic metapelites, Paleoproterozoic gneisses and migmatites and Archean greenstone belts pervasively intruded by TTG granitoids. The latter are compartmentalized by lithospheric-scale Archean – Paleoproterozoic shear zones with a general sub-vertical fabric. Upon extension, these pre-existing shear zones nucleated extensional deformation, focalized magmatism and accommodated different rates of extension and width of offshore rift domains. In the north, younger Neoproterozoic lithospheric domain deformed with a ductile behavior and multiple crustal detachments promoting lithospheric decoupling and a distributed extension, with late continental break-up. It favored the formation of a wide magma-poor margin where extension was accommodated by low-angle, seaward-dipping extensional faults and mantle-exhumation. To the south, Archean and Paleoproterozoic lithospheric domain with stronger and brittle strength profile promoted a more localized extensional deformation and favored an early lithospheric coupling and continental break-up. This ultimately led to the formation of a short margin with increased magmatic budget, where extension was accommodated by high-angle, landward-dipping extensional faults and mantle-exhumation. We demonstrate that the pre-rift heterogeneity of the lithosphere controlled the mode of extension during the rift and the along-strike variation of margin geometry. Moreover, the rejuvenation of Precambrian shear zones as extensional transverse fault zones also promoted the activation of lithospheric-scale thermal drains facilitating the emplacement of mantle-related melts into the upper crust.