Avalonia is the largest accreted crustal block in the Appalachian orogen and comprises a collection of late Neoproterozoic volcano-sedimentary sequences that are overlain by a Palaeozoic platformal sedimentary succession. Detrital zircons from the Conception Group are dominated by 570-620 Ma ages and contain a significant component generated by erosion of coeval igneous arc-volcanic rocks. Overlying samples from the Cuckold and Crown Hill formations are dominated by Neoproterozoic populations with ages between 600 and 650 Ma and are interpreted to be derived from the underlying calc-alkaline arc-plutonic rocks. Early Palaeozoic platform units are dominated by c. 620 Ma zircons with lesser Mesoproterozoic and Palaeoproterozoic zircons. The range of detrital zircon ages is inconsistent with a West African provenance and suggests that Avalonia originated along the Gondwanan margin of the Amazon craton. The influx of Mesoproterozoic and Palaeoproterozoic detritus in the Avalonian platform suggests a major change in tectonic regime. The prominent change in provenance is interpreted to be related to separation of Avalonia from Gondwana during the Early Ordovician opening of the Rheic Ocean. The Redmans Formation is interpreted to represent the rift-drift transition of the Rheic Ocean, which imposes important constraints on the palaeotectonic evolution of Avalonia.