High-sulfidation vein gold deposits such as El Indio, Chile, formed in fracture arrays <1000m beneath paleo-solfatara in volcanic terranes. Stable isotope data have confirmed a predominance of magmatic vapor during the deposition of arsenic-rich sulfide-sulfosalt assemblages in this deposit. These provide a unique opportunity to analyze the processes and products of high-temperature volcanic gas expansion in fractures that form the otherwise inaccessible infrastructure deep inside equivalent present-day fumaroles. We provide field emission scanning electron microscope and LA-ICP-MS micro-analytical data for the wide range of heavy, semi-metals and metalloids (arsenic, antimony, bismuth, tin, silver, gold, tellurium and selenium) in the complex pyrite-enargite-Fe-tennantite assemblages from Copper Stage mineralization in the El Indio deposit. These data document the progressive fractionation of antimony and other heavy metals, such as bismuth, during crystallization from a sulfosalt melt that condensed from expanding vapor at about 15MPa (150bars) and >650°C following higher temperature vapor deposition of crystalline pyrite and enargite. The sulfosalt melt aggressively corroded the earlier enargite and pyrite and hosts clusters of distinctive euhedral quartz crystals. The crystallizing sulfosalt melt also trapped an abundance of vugs within which heavy metal sulfide and sulfosalt crystals grew together with K-Al silicates and fluorapatite. These data and their geologic context suggest that, in high-temperature fumaroles on modern active volcanoes, over 90% of the arsenic content of the primary magmatic vapor (perhaps 2000mgkg -1) was precipitated subsurface as sulfosalt. Subsurface fractionation may also account for the range of exotic Pb-Sn-Bi-Se sulfosalts observed in fumarole sublimates on active volcanoes such as Vulcano, Italy, as well as on extra-terrestrial volcanoes such as Maxwell Montes, Venus.