Earth’s only active natrocarbonatite volcanism, occurring at Oldoinyo Lengai (OL), Tanzania, suggests that natrocarbonatite melts are formed through a unique geological process. In the East African Rift, the extinct Kerimasi (KER) volcano is a neighbor of OL and also contains nephelinites hosting melt and fluid inclusions that preserve the igneous processes associated with formation of natrocarbonatite melts. Here, we present evidence for the presence of coexisting nephelinite melt, fluorine-rich carbonate melt, and alkali carbonate fluid. The compositions of these phases differ from the composition of OL natrocarbonatites; therefore, it is unlikely that natrocarbonatites formed directly from one of these phases. Instead, mixing of the outgassing alkali carbonate fluid and the fluorine-rich carbonate melt can yield natrocarbonatite compositions at temperatures close to subsolidus temperatures of nephelinite (<630–650 °C). Moreover, the high halogen content (6–16 wt%) in the carbonate melt precludes saturation of calcite (i.e., formation of calciocarbonatite) and maintains the carbonate melt in the liquid state with 28–41 wt% CaO at temperatures ≥600 °C. Our study suggests that alkali carbonate fluids and melts could have commonly formed in the geological past, but it is unlikely they precipitated calcite that facilitates fossilization. Instead, alkali carbonates likely precipitated that were not preserved in the fossil nephelinite rocks. Thus, alkali carbonate fluids and melts have been so far overlooked in the geological record because of the lack of previous detailed inclusion studies.