Oldoinyo Lengai in the Tanzanian rift valley is the only active carbonatite volcano in the world and its natrocarbonatitic lavas are unique in composition. The characteristics of effusive natrocarbonatite activity in June 1988 were studied and fresh samples were directly collected from active carbonatitic lava lakes and flows. Analyses of these samples provide the first information on natrocarbonatites since these unusual volcanic rock type was first described from the 1960 1961 eruptions. The analytical results constrain the original chemistry of fresh natrocarbonatite. Temperatures in lava lakes and of carbonatite lava flows range 491 544°C. The natrocarbonatite lava is extremely fluid at these temperatures and reaches incandescence. The most common variety of natrocarbonatite is porphyritic with abundant phenocrysts of nyerereite (Na0.82K0.19)2(Ca, Sr, Ba)0.975(CO3)2 and gregoryite Na1.74K0.1(Ca, Sr, Ba)0.16CO3, with complex substitution of (CO3)2- by (SO4)2-, (PO4)3-, F-, and Cl-. A phenocryst-poor to aphyric natrocarbonatite variety reflects residual liquids separating from the crystal-rich porphyritic flows. Sylvite, fluorite, and Fe-alabandite (Mn0.7Fe0.3S) have been identified as additional primary magmatic phases. Rare phases in the matrix are witherite (BaCO3) and sellaite (MgF2). Sylvite and gregoryite, and to a lesser extent nyerereite, are water-soluble and are responsible for the immediate decomposition and chemical alteration of natrocarbonatites under atmospheric conditions. A peralkaline combeite-bearing nephelinite lava is closely related to the natrocarbonatite activity, and is isotopically indistinguishable. It is likely that these two magma compositions are related by liquid immiscibility. The unusual hyperalkaline composition of both magma types makes Oldoinyo Lengai an exotic volcano, and its carbonatites have extreme compositions, and are not representative of carbonatites in general.