The Devonian/Carboniferous Boundary (DCB) interval is associated with mass extinction, isotope excursions and a short glacial episode. This study investigates how boundary extinction and environmental change is expressed in the glacial high-palaeolatitudinal record of the Bolivian Altiplano (western Gondwana). A latest Devonian and early Carboniferous section has been investigated using sedimentology, palynology, total organic carbon and bulk δ13Corganic. The Colpacucho Formation is a Late Devonian shelfal–marine siliciclastic sequence. It is overlain in the study area by a unit of coarse sandstones and sandy diamictites, interpreted as glaciomarine. This distinctive glaciomarine unit is at least 7 km wide and 60–120 m thick with a variably incisive basal contact (<100 m). It is of very latest Famennian age and is a stratigraphic equivalent of proven glacigenic deposits across central South America. The offshore marine Kasa Formation overlies the glacigenic unit above a basal flooding surface. The DCB is 12 m above this flooding surface on the last occurrence of Retispora lepidophyta and significant palynological assemblage changes. This includes the loss of the Umbellasphaeridium saharicum phytoplankton bioprovince, endemic to Gondwana. Marine and terrestrial palynological extinctions are synchronous with a 2 ‰ positive carbon isotope excursion interpreted to be reflective of changes in organic matter delivery and preservation during an interval of environmental stress. These results inform wider debates on global environmental change and mass extinction at the DCB.