Nine Namurian clay bands retrieved from boreholes in the northern part of the Pennine Basin are, on the basis of their petrography, mineralogy and geochemistry, shown to be volcanic in origin and are therefore bentonites. The bentonites, which have a fragmental texture, are normally graded and show rare preservation of shard textures, representing vitric tuff deposits that have been altered subsequently to clay‐dominated horizons. Crystals are a minor component of the bentonites, but biotite, in particular, is concentrated at the base of the beds. A clay mineral assemblage of mixed‐layer illite–smectite with subordinate kaolinite identifies most of the samples as K‐bentonites, but kaolinite dominates two samples that can be classed as tonsteins. Temporal variation of salinity within the depositional basin is suggested to explain these different clay assemblages. The major element geochemistry of the bentonites reflects their clay mineralogy and the compositions of diagenetic minerals present, the latter including pyrite, carbonates and hydroxyapatite. Enrichment of the bentonites in some trace elements (including Ba, Sr, Pb, Cu and Ni) can be related to the presence of the diagenetic minerals, but the extent to which the elements are added from external sources as opposed to being redistributed within the ash is unclear. Immobile trace element systematics suggest a rhyodacite/dacite composition for the original ash and derivation from the collision of plates, this being supported by evidence provided by the rare earth elements (REE) in one group of samples. However, in another group of samples, variations in REE concentrations may be caused by mobility of these elements during alteration. The chemistry of the Namurian bentonites contrasts markedly with that of the local Carboniferous volcanics but is comparable, in some respects, with one group of Westphalian tonsteins, although the latter are more rhyolitic in character. It is suggested that the Namurian bentonites and the Westphalian tonsteins of acid affinities originated from volcanic activity associated with a destructive plate margin in the Variscan externides and that the observed compositional trend may reflect magma evolution possibly related to the progressive east–west closure.