The Precambrian geology of eastern Zambia and Malawi is highly complex due to multiple episodes of rifting and collision, particularly during the formation of Greater Gondwana as a product of the Neoproterozoic Pan-African Orogeny. The lithospheric structure and extent of known Precambrian tectonic entities of the region are poorly known as there have been to date few detailed geophysical studies to probe them. Herein, we present results from electromagnetic lithospheric imaging across Zambia into southern Malawi using the magnetotelluric method complemented by high-resolution aeromagnetic data of the upper crust in order to explore the extent and geometry of Precambrian structures in the region. We focus particularly on determining the extent of subcontinental lithospheric mantle (SCLM) beneath the Archean-Paleoproterozoic cratonic Bangweulu Block and the Mesoproterozoic-Neoproterozoic Irumide and Southern Irumide Orogenic Belts. We also focus on imaging the boundaries between these tectonic entities, particularly the boundary between the Irumide and Southern Irumide Belts. The thickest and most resistive lithosphere is found beneath the Bangweulu Block, as anticipated for stable cratonic lithosphere. Whereas the lithospheric thickness estimates beneath the Irumide Belt match those determined for other orogenic belts, the Southern Irumide Belt lithosphere is substantially thicker similar to that of the Bangweulu Block to the north. We interpret the thicker lithosphere beneath the Southern Irumide Belt as due to preservation of a cratonic nucleus (the pre-Mesoproterozoic Niassa Craton). A conductive mantle discontinuity is observed between the Irumide and Southern Irumide Belts directly beneath the Mwembeshi Shear Zone. We interpret this discontinuity as modified SCLM relating to a major suture zone. The lithospheric geometries determined from our study reveal tectonic features inferred from surficial studies and provide important details for the tectonothermal history of the region.