A pioneer study of the previously unknown δ13C chemostratigraphy in the Ordovician/Silurian boundary interval in eastern Iowa and northeastern Illinois resulted in the discovery of the Hirnantian Isotope Carbon Excursion (HICE). The presence of this major isotope excursion in the Mosalem Formation in Iowa and the Wilhelmi Formation in Illinois, which indicates that the excursion interval in these units is of Hirnantian (latest Ordovician) rather than Early Silurian age, necessitates a revised chronostratigraphic classification of these units. Although the precise level of the Ordovician/Silurian boundary remains somewhat uncertain in the absence of the diagnostic graptolites, it is herein placed in the upper part, but well below the top, of the Mosalem Formation and at the top of the Wilhelmi Formation. During a major regression following the deposition of the Maquoketa Shale, the upper part of the latter clastic unit was in some places deeply eroded, resulting in a topographically dissected landscape with upland areas separated by wide incised valleys. During a subsequent late Hirnantian transgression, these palaeovalleys were gradually filled with marine sediments, but the upland areas were not transgressed until earliest Silurian times. The new chemostratigraphical evidence is in good agreement with the available biostratigraphical data, especially from corals, conodonts, and brachiopods. A preliminary chemostratigraphical study of the presumably coeval Edgewood Group successions in Pike County, northeastern Missouri failed to document any heavy δ13C values characteristic of the HICE and some, or all, of the Hirnantian values obtained there may be diagenetically overprinted.