The Zonguldak terrane is a Gondwana-derived continental microplate along the Black Sea coast in northwest Anatolia. It includes a Cadomian basement, with oceanic- and island-arc sequences, unconformably overlain by siliciclastic rocks of Ordovician to Middle Silurian age. After a period of deformation and erosion, late Lower Devonian (Emsian) quartzites and shallow-marine limestones unconformably cover Middle Silurian (Wenlock) graptolitic shales. Along several cross sections across the unconformity plane, the mineralogical characteristics of the Paleozoic sedimentary rocks in the Zonguldak terrane are studied to check whether this regional unconformity is only of epeirogenic nature or the result of a thermal event. In addition to the appearance of kaolinite in Devonian units, crystal-chemical data of illites show a sudden jump at the unconformity plane. The b cell dimension values of illites of Ordovician–Silurian units are somewhat higher than those of Devonian–Carboniferous units and show a drastic drop between the Silurian and Devonian units. The new mineralogic data indicate that the pre-Emsian rocks in the Zonguldak terrane experienced a thermodynamo event, prior to the Emsian transgression. This Caledonian-time event is also reported in east Moesian terrane but not noticed in the neighboring Istanbul–Zonguldak and in the west Moesian – Balkan – Kreishte terranes. By this, it is suggested that Zonguldak and east Moesian terranes behaved independently from the Istanbul–Balkan terranes during the closure of the Rheic Ocean. They very likely docked to Laurussia during Emsian by strike-slip faults and remained thereon at its platform margin, where the Middle–Late Devonian shallow-platform conditions were followed by fluvial (lagoon and delta) conditions and deposition of coal during Late Carboniferous.