Tectonic fractures in Palaeozoic strata of the Kinshasa area, DR Congo, locally host palygorskite-bearing veins and associated calcite occurrences. The palygorskite deposits are typically massive, with a varying degree of alignment of clay particles, a higher quartz content than the arkose substrate, and a variable amount of smectite (montmorillonite). The associated calcite occurrences are macrocrystalline coatings and infillings, and more fine-grained calcite veins with cataclastic texture. The calcite coatings and infillings formed from solution in earth surface conditions, as recorded by their stable isotope signature. The palygorskite-dominated deposits in the fractures formed at a later stage, in a setting without indications of authigenic mineral formation related to hydrothermal activity or to low-temperature interaction of solutions with the local substrate. The veins most likely formed by vertical infiltration of suspended matter in fractures that extended to a post-Palaeozoic palaeosurface, during or after deposition of palygorskite-bearing Upper Jurassic to Early Cretaceous sediments. This represents an exceptional mode of palygorskite vein development, unrelated to any form of mineral authigenesis that is typically invoked to explain vein-type occurrences of palygorskite and related minerals.