At the historical Eskeborner Berg underground workings at Tilkerode (Eastern Harz Mountains, Germany), Fe was mined from a carbonate–hematite vein system that was locally enriched in selenide minerals. Clausthalite [PbSe] was the most abundant selenide mineral in a carbonate matrix with laths of specular hematite. To date, the selenide-bearing carbonate–hematite vein system at Tilkerode has not been geochemically investigated. Here, we present the first whole-rock chemical data for a wide suite of trace elements. The following metals are enriched relative to bulk continental crust (orders of magnitude in parentheses): Se (>105), Hg (>104), Ag and Pb (103), Au, Bi, Pt, Ge, Te, Pd and Cd (102). Samples from Tilkerode have up to 2640 ppm Ag, 338 ppm Ge, 1560 ppb Au, 970 ppb Pt and 365 ppb Pd, with Pt/Pd > 1, and a significant positive correlation of Ge vs. (Pd+Pt). The selenide mineralisation took place below 112 °C, the maximum temperature stability of umangite [Cu3Se2]. Our data indicate there is potential for prospecting Ge and precious metals in low-temperature vein systems