This study describes the occurrences of sulfate minerals in mines of the Czech part of the Upper Silesian Basin. This mineralization originates from the oxidation of Fe disulfides contained in the coal matrix and enclosing sediments. The oxidation occurs in the presence of formational brines and chemotrophic bacteria. The brines have a pH between 6.3 and 8.5 and total solute content of up to 300 g/l. They are rich in Na, Ca, K, Mg, Ba and Sr and Cl− is the major anion. The minerals of the pickeringite–halotrichite series with coexisting magnesiocopiapite are formed primarily in drier places and areas where the water is only slightly mineralized. In more humid places where the brines are more concentrated, a diverse assemblage of up to 20 different sulfates are found (e.g. natrojarosite, sideronatrite, metasideronatrite, tamarugite, magnesiocopiapite, bílinite, starkeyite, blödite, rozenite and siderotil). These sulfates are accompanied by halite, sulfur, goethite and a number of phases of uncertain identity, such as sulfates containing Sr and REE. This is an example of mineral paragenesis formed by weathering in a saline evaporite environment, which is extremely rare in Europe but is found in arid regions elsewhere (e.g. in the Atacama Desert in Chile).