At Roter Bar, a former underground mine in the polymetallic deposits of St. Andreasberg in the middle-Harz vein district, Germany, native gold and palladium minerals occur very locally in clausthalite–hematite pockets of few millimetres across in carbonate veinlets. The native gold is a Au–Ag intermetallic compound and the palladium minerals are characterised as mertieite-II [Pd8(Sb,As)3] and empirical PdCuBiSe3 with some S. The latter coexists with bohdanowiczite (AgBiSe2), a mineral that is stable below 120 °C. The geological setting of Roter Bar, underneath a post-Variscan unconformity, and its hematite–selenide–gold association suggest that oxidising hydrothermal brines of low temperature were instrumental to the Au–Pd mineralisation. The Roter Bar Au–Pd mineralisation can be explained by Permo-Triassic, red-bed-derived brines in the context of post-Variscan, unconformity-related fluid overprint.