The incipient phases of continental rift development remain enigmatic, as early rift sequences are rarely exposed, or poorly preserved in the geologic record. Here, we present petrographic and geochemical analyses of heavy mineral separates from pervasively weathered volcanic horizons intercalated within syn-rift sedimentary deposits from the Rukwa Rift Basin, southwestern Tanzania. These Oligocene (25–26 Ma) ashfalls represent the first magmatic products associated with the initiation of rifting in the western branch of the East African Rift System (EARS). In this work, we combine detailed single crystal petrography with in-situ geochemistry to characterise an alkaline volcanic mineral assemblage consisting of titanite, phlogopite, fluorapatite, clinopyroxene, Ti-rich andradite, sanidine, pyrochlore, nepheline, cancrinite, Fe-sulphide (pyrrhotite), calcite, Na-REE‑carbonate and peralkaline silicate melt. These minerals are significantly enriched in trace elements, particularly Ba, Sr and rare earth elements (REE), with REE + Y contents consistent with derivation from peralkaline phonolitic melts. Placed in context of EARS development, these tuffs display the hallmarks of explosive alkaline‑carbonatite volcanism in their resistant minerals and inclusions; the nature and occurrence of which is consistent with early rift progression elsewhere in the EARS. Importantly, we showcase the depth of extractable petrographic information preserved in extensively weathered volcanic ash horizons deposited into an active continental rift basins. Such an approach may have significant implications for recognising early volcanogenic sequences in continental rift zones worldwide, but particularly in other segments of the western branch of the EARS.