Late Tertiary-Quaternary volcanism around Calatrava, within the Hercynian massif of central Spain, is alkaline mafic-ultramafic, with ∼250 centres, mainly monogenetic cones and vents, with melilitite the most abundant eruptive. Carbonatite may be expected in association with melilitite and a clear example of magmatic carbonate emerged from a brief field reconnaissance. It is a vent filled with a mixed eruption of glassy melilitite lapilli in a carbonate matrix. Levels and profiles of trace elements are inseparable from recognized carbonatite, and totally unlike those in local sedimentary limestone and caliche. C and O isotopes are the same as those reported for carbonatite ashes in other provinces. Carbonate is present as globules in the melilitite glass, and as inclusions within large clinopyroxene and olivine grains, which are largely xenocrystic. Euhedral spinels in melilitite and carbonate matrix are chromite mantled with titano-magnetite, reported previously only from high-temperature kimberlite. Wehrlite fragments indicate direct eruption from the mantle. Phlogopite and chromian spinel are found only as inclusions in the olivine, pointing to a phlogopite-carbonate mantle source region of the type favoured for carbonatite and melilitite melt generation. Calatrava represents the most southerly and westerly expression in mainland Europe of intra-continental carbonatite-melilitite volcanism. Follow-up field visits have shown that carbonate volcanism is extensive and voluminous throughout the province, requiring a long-term research programme.