Black shales may serve as an important source of metals such as Co, Ni, or As, largely due to anoxic to euxinic conditions in association with high concentrations of sulfur leading to efficient scavenging and transport of metals from seawater into the seafloor sediment. We report on an unusual type of Au mineralization newly discovered in Ediacaran trench-slope black shales in the Bohemian Massif, Czech Republic. The Au enrichment is related to the formation of a quartz–sulfide vein system and a progressive evolution of ore-forming fluids with decreasing temperature, from Sb- to As-rich to final precipitation of native gold from silica and Au-bearing low-temperature hydrothermal colloidal solutions. The hydrothermal nature of these solutions is also documented by Li contents and isotope compositions which differ markedly between barren black shales and those carrying significant late-stage quartz-rich veins. The structural relationships and orientation of the associated quartz veins point to a close connection between vein emplacement and high heat flow in response to Ordovician rifting, and breakup of the northern margin of Gondwana, and opening of the Rheic Ocean. This triggered metal and sulfur remobilization, including Au, from the associated Neoproterozoic–Cambrian volcanosedimentary successions. The documented Au mineralization and its association with the Ordovician rift-related magmatic activity is different from the widespread Variscan Au occurrences in the Bohemian Massif. Our study thus provides a new genetic model potentially important for future exploration of Au also in other terrains underlain by a rifted Cadomian basement.