Genthelvite from pegmatite veins hosted by the albite-enriched granite (ca.1.8 Ga) corresponding to the Sn–Nb–Ta (F, REE, Li, Zr, U, Th) Madeira deposit, Amazonas, Brazil was studied. Genthelvite, the exclusive Be-bearing mineral within the deposit, occurs as massive crystals of up to 4.7 cm in size. Compositions are homogeneous within individual crystals, although there is moderate variation in the overall composition reflecting relatively limited substitutions within the helvine–genthelvite–danalite solid-solution series, with relatively high Zn contents (36.96 to 49.45 wt.% ZnO), lower Mn contents (0.61 to 3.03 wt.% MnO), and variable Fe contents (2.10 to 10.94 wt.% FeO), completing an existing compositional gap in this system. Genthelvite formed in an alkaline and subaluminous environment, under stable conditions within the late-evolved fluids, at relatively high temperature (>400°C), in a reducing environment. The extremely high concentration of fluorine in the magma and the crystallisation of magmatic galena resulted in an effective reduction of H2S fugacity. This resulted in the stabilisation of genthelvite during the transition from the late magmatic to early hydrothermal stages of the albite-enriched granite evolution. The variability in Fe content within genthelvite is associated primarily with localised variations in the mineral assemblage (e.g. the presence of riebeckite and polylithionite). Genthelvite was altered by low-temperature aqueous fluids rich in F which resulted in the incorporation of Fe, Mn, Mg, Pb, Ba, Na, K, U and REE into the Zn2+ structural site and the allocation of excess Si, Al, Ti and P in the IVSi and IVBe structural sites. The substantial content of U and REE substituting for Zn, together with Si substituting for Be, is charge balanced by the presence of vacancies at the A site.