The NYF La Elsa pegmatite forms a subcircular, ∼30 m long, ∼20 m wide body enclosed in the parental Potrerillos granite, Las Chacras-Potrerillos batholith, Argentina. The pegmatite has a typical zonal internal structure with a volumetrically significant quartz core and pods of magmatic fluorite. Along with biotite, mostly in the outer units, tourmaline (schorl, fluor-schorl) is common to abundant in most pegmatite units. Accessory minerals include common strongly hematitized ilmenite and rare euhedral crystals of bismuthinite, up to 2 cm long, occurring at the transition between the blocky zone and the quartz core. The bismuthinite was significantly replaced by bismutite I according to the reaction Bi2S3(s) + CO2(aq) + 6O2(aq) + 3H2O(l) = Bi2CO3O2(s) + 3H2SO4(aq). Subsequently, bismutite I was replaced by bismutite II and kettnerite. The former requires an influx of Ca and F and its formation can be characterized by the reaction Bi2CO3O2(s) + 2Ca2+(aq) + 2F–(aq) + CO32–(aq) = 2CaBiCO3OF(s). At the late hydrothermal stages bismutite was replaced by clinobisvanite/pucherite during influx of V according to the reaction Bi2CO3O2s + 2H3VO4(aq) = 2BiVO4(s)+ CO2(aq) + 3H2O(l). All Bi minerals are close to the ideal formulae with only minor Pb and ±Cu in bismuthinite and its secondary products. The crystallization sequence of Bi minerals is magmatic bismuthinite (S2–) → early hydrothermal bismutite I (CO32–) → medium stage bismutite II + kettnerite (CO32–, F–) → late stage clinobisvanite, pucherite (VO43–). Pegmatite-derived early subsolidus fluids were enriched in CO2, which was confirmed by confocal Raman microspectroscopy of fluid inclusions in quartz and caused breakdown of bismuthinite to bismutite. Calcium and F, necessary for kettnerite formation, were released during alteration of magmatic fluorite at acidic conditions. Vanadium was supplied by meteoritic H2O enriched in elements from altered magmatic minerals (biotite, ilmenite), either from the pegmatite or from the host granite.