This paper is included in the Special Publication entitled 'The proto- Andean margin of Gondwana', edited by R.J. Pankhurst and C.W. Rapela. Ordovician K-bentonites have now been recorded from >20 localities in the vicinity of the Argentine Precordillera. Most occur in the eastern thrust belts, in the San Juan Limestone and the overlying the Gualcamayo Formation, but a few ash beds are known also from the central thrust belts. The oldest occur in the middle Arenig I, victoriae lunatus graptolite (Oe. evae conodont) Zone, and the youngest in the middle Llanvirn P. elegans (P. suecicus) Zone. Mineralogical characteristics, typical of other Ordovician K-bentonites, include a matrix of illite/smectite mixed-layer clay and a typical felsic volcanic phenocryst assemblage: biotite, beta-form quartz, alkali and plagioclase feldspar, apatite, and zircon, with lesser amounts of hornblende, clinopyroxene, titanite and Fe-Ti oxides. The proportions of the mineral phases and variations in their crystal chemistry are commonly unique to individual (or small groups of) K-bentonite beds. Glass melt inclusions preserved in quartz are rhyolitic in composition. The sequence is unique in its abundance of K-bentonite beds, but a close association between the Precordillera and other Ordovician sedimentary basins cannot be established. The ash distribution is most consistent with palaeogeographical reconstructions in which early Ordovician drifting of the Precordillera occurred in proximity to one or more volcanic arcs, and with eventual collision along the Andean margin of Gondwana during the mid-Ordovician Ocloyic event of the Famatinian orogeny. The Puna-Famatina terrane northeast of the Precordillera might have served as the source of the K-bentonite ashes, possibly in concert with active arc magmatism on the Gondwana plate itself.