A `metamorphic vermiculite'-like phase was identified in Ca-rich ancient ceramic sherds from excavations in NW Peloponnese, Greece. Archaeometric investigations have shown that the raw materials used in the production of ancient ceramics were derived from local Plio-Pleistocene sediments. Analysis by X-ray diffraction and scanning electron microscopy-energy dispersive spectroscopy showed that `metamorphic vermiculite' is a common constituent phase of these sediments occurring in three texturally different types: as interstratified white mica-chlorite and chlorite-vermiculite, and white mica-(white mica-chlorite) stacks. In an attempt to elucidate the thermal transformation of `metamorphic vermiculite' present in the calcareous raw materials, we produced experimental ceramics made from these local raw materials and fired them at 700, 750, 850, 950 and 1050°C in a static air furnace. The mixed-layered chlorite-vermiculite was transformed completely at ∼800°C contributing to the formation of new high-T minerals. The two other types of `metamorphic vermiculite' retain their original lath-like shape up to 1050°C and only a few crystals show that they have undergone complete transformation at this temperature. In the latter crystals, numerous nanocrystals were formed sub-parallel to the former cleavages of `metamorphic vermiculite' pseudomorphs, suggesting their contribution to the nucleation of high-T minerals (i.e. ferrian aluminian diopside, spinel, Fe oxides) by reactions with the available CaO. It is suggested that the firing conditions (i.e. maximum reaction temperature of 1050°C, reaction time of 1 h, oxygen atmosphere) which promote disequilibrium reactions, and the greater contribution of the white mica constituent against chlorite in some of the initial structures of `metamorphic vermiculite' may be responsible for the delay of its thermal decomposition at 1050°C.