The vast Laptev and East Siberian shelves in the eastern Russian Arctic, largely covered by a shallow sea and buried beneath sea ice for 9months of the year, remain one of the least studied parts of continental crust of the Earth and represent a big unknown when performing pre-Cenozoic reconstructions of the Arctic. The De Long Islands provide an important window into the geology of this area and are a key for understanding the Early Paleozoic history of the Amerasian Arctic. Four of them (Jeannette, Henrietta, Bennett and Zhokhov islands) were studied using structural data, petrographic and geochemical analyses and U–Pb zircon age dating to offer the following new constraints for the Early Paleozoic paleogeography of the Arctic realm. The basement beneath the De Long Islands is of Late Neoproterozoic to earliest Cambrian age, about 670–535Ma. In the Early Paleozoic, the De Long Islands were located along the broad Timanian margin of Baltica, with a clastic sediment provenance from the Timanian, Grenville–Sveconorwegian, and Baltic Shield domains. The Cambro-Ordovician volcaniclastic successions on Jeannette and Henrietta islands formed part of a continental volcanic arc with a corresponding back-arc basin located to the south (in present co-ordinates). On the continent-ward side of the back-arc basin, shallow marine shelf clastic and carbonate rocks were deposited, which are exposed today on Bennett Island in the south-west of the archipelago (in modern coordinates). The De Long Islands together with other continental blocks, such as Severnaya Zemlya, Arctic Alaska–Chukotka, and the Alexander Terrane, formed the contiguous active continental margin of Baltica during the Early Paleozoic. Today however, these terranes are spread out over a distance of 5000km across the Arctic and eastern Pacific margins due to the subsequent opening of a series of Late Paleozoic, Mesozoic and Cenozoic oceanic basins.