The carbon and oxygen isotope composition of marine carbonates (δ13C and δ18O, respectively) are studied in the fossiliferous, stratigraphically well-constrained and remarkably expanded successions of Podolia, SW Ukraine, spanning the Silurian–Devonian transition. Significant isotopic shifts are directly comparable to previously published global secular trends in well-preserved brachiopod calcite isotopic ratios from this region, and therefore may be taken as a reliable primary record of seawater δ13C changes. The sections reveal a major positive δ13C excursion, with an amplitude above 6 ‰, beginning in the upper Pridoli and reaching peak values as heavy as +4.2 ‰ in the lowermost Lochkovian. This turnover in carbon cycling is followed by a general trend toward more negative δ13C values in the upper Lochkovian. The Podolian isotopic signals provide strong support for the previously inferred global biogeochemical perturbation across the Silurian–Devonian transition, reflecting a complex combination of palaeogeographical, biogeochemical and evolutionary processes in the late Caledonian geodynamic setting, with a likely undervalued role of the expanding vegetation in vast near-coastal shallows and deltas.