Gold mineralization at the Viceroy Mine is hosted in extensional veins in steep shear zones that transect metabasalts of the Archaean Arcturus Formation. The gold mineralization is generally made up of banded or massive quartz carrying abundant coarse arsenopyrite. However, most striking is a distinct suite of Au-Bi-Te-S minerals, namely joseite-A (Bi4TeS2), joseite-B (Bi4Te2S), hedleyite (Bi7Te3), ikunolite (Bi4S3), ‘protojoseite’ (Bi3TeS), an unnamed mineral (Bi6Te2S), bismuthinite (Bi2S3), native Bi, native gold, maldonite (Au2Bi), and jonassonite (AuBi5S4). The majority of the Bi-Te-S phases is characterized by Bi/(Se+Te) ratios of >1. Accordingly, this assemblage formed at reduced conditions at relatively low fS2 and fTe2. Fluid-inclusion thermometry indicates depositional temperatures of the main stage of mineralization of up to 342°C, in the normal range of mesothermal, orogenic gold deposits worldwide. However, melting temperatures of Au-Bi-Te phases down to at least 235°C (assemblage (Au2Bi + Bi + Bi7Te3)) imply that the Au-Bi-Te phases have been present as liquids or melt droplets. Furthermore, the close association of native gold, native bismuth and other Bi-Te-S phases suggests that gold was scavenged from the hydrothermal fluids by Bi-Te-S liquids or melts. It is concluded that a liquid/melt-collecting mechanism was probably active at Viceroy Mine, where the distinct Au-Bi-Te-S assemblage either formed late as part of the main, arsenopyrite-dominated mineralization, or it represents a different mineralization event, related to rejuvenation of the shear system. In either case, some of the gold may have been extracted from pre-existing, gold-bearing arsenopyrite by Bi-Te-S melts, thus leading to an upgrade of the gold ores at Viceroy. The Au-Bi-Te-S assemblage represents an epithermal-style mineralization overprinted on an otherwise mesothermal (orogenic) gold mineralization.