The Demerara Rise is a prominent bathymetric feature that has been considered as a broad expression of shallow continental basement and used in conjunction with the Guinea Plateau as a pinning point for circum-Atlantic plate reconstructions. Previously, shallow-penetration, poorly imaged seismic data over the Demerara Rise were modeled with the lower sequences interpreted as continental crust at relatively shallow depths. However, new long-offset, deeply penetrating seismic data provide evidence that basement nearly or entirely comprises excessively thick volcanic strata (approximately 21 km). Seismic character and geometry, 2D gravity modeling, and volcanic margin analogs were used to identify unfaulted, convex-upward seaward dipping reflector (SDR) packages. These steeply dipping (approximately 20°) igneous successions are westwardly divergent, and occur as offlapping reflector sets in trains as long as 250 km. This rift-related volcanism now recognized at the Demerara Rise was probably conjugate to syn-rift volcanism in South Florida/Great Bahama Bank, and from this we have predicted a volcanic element for the Guinea Plateau. This volcanism could be linked to a Bahamas hot spot at the initial opening of the Central Atlantic. Six SDR packages have been interpreted below the Late Jurassic-Early Cretaceous carbonate section of the rise, indicating that the early volcanism produced a marine substrate upon which the subsequent carbonate bank section developed. We have inferred that this Early Cretaceous volcanic/carbonate margin continued into the Guinea Plateau of West Africa. The pre-Aptian section was inverted and peneplained with a strong angular unconformity prior to the Early Cretaceous opening of the Equatorial Atlantic seaway. The newly identified Central Atlantic volcanic margin of the Demerara Rise holds implications of a volcanic origin for its conjugate margins. We have confirmed a voluminous magma-rich opening of the southeastern Central Atlantic.