The diagenetic to very low-grade metamorphic manganese ores of the Postmasburg manganese field provide a unique example of oxide-facies manganese ores in a Palaeoproterozoic palaeokarst setting. The ores are composed mainly of braunite group minerals, including braunite, partridgeite and bixbyite, with rare braunite II and Ca-poor, silica-depleted braunite. Iron-poor partridgeite is distinguished from Fe-rich bixbyite and the occurrence of Ca-poor, silica-depleted braunite is reported for the first time. Braunite and partridgeite formed during early diagenesis but remained stable under greenschist facies metamorphic conditions. In contrast, bixbyite is apparently a product of metasomatic remobilisation under peak metamorphic conditions. It is suggested that local variations of the metamorphic mineral association reflect variations of the host rock composition and that they are not related to changing P-T conditions of metamorphic alteration, a model promoted by previous authors. The phase chemistry of braunite, braunite II and bixbyite is explained by the existing polysomatic stacking model for the braunite group. However, the chemical composition of partridgeite and Ca-poor, silica-depleted braunite can only be explained by introducing a distinct module layer, with partridgeite composition, to the existing polysomatic stacking model.