Selenium-rich Au-Ag mineralization has been discovered in the Kremnica ore district, central Slovakia. The mineralization is hosted by a single quartz-dolomite vein hosted by Neogene propyllitized andesites of the Kremnica stratovolcano. Ore mineralogy and crystal chemistry of individual ore minerals have been studied here. The early base-metal ore mineralization composed of pyrite, sphalerite and chalcopyrite lacks selenium, whereas the superimposed Au-Ag paragenesis is Se-enriched. The Au-Ag alloys, uytenbogaardtite, minerals of the galena-clausthalite series, acanthite-naumannite series, diaphorite, miargyrite, pyrargyrite-proustite, polybasite group, minerals of the tetrahedrite group and andorite branch (andorite IV, andorite VI, Ag-excess fizélyite), freislebenite, and rare Pb-Sb sulphosalts (scaiinite, robinsonite, plagionite) have been identified here. Besides selenides, the most Se-enriched phases are miargyrite, proustite-pyrargyrite, and polybasite-pearceite, whose Se contents are among the highest reported worldwide. In addition, one new phase has been found, corresponding to a Se-analogue of pearceite containing 2.08 - 3.54 apfu Se. The style of mineralization, paragenetic situation, and chemical trends observed in individual minerals are comparable to those of Au-Ag low-sulphidation epithermal Au-Ag mineralizations of the Kremnica and neighboring Štiavnica and Hodruša-Hámre Ore Districts, however, the pronounced enrichment in selenium is a specific feature of the studied vein only.