Palaeozoic volcanism in the Avalon Terrane of northern Nova Scotia occurred during three time intervals: Cambrian–early Ordovician, late Ordovician–early Silurian and middle–late Devonian. In the Meguma Terrane of southern Nova Scotia, Palaeozoic volcanism is limited to the middle Ordovician. Geochemical data show that most of these volcanic rocks are bimodal, within-plate suites. Initial εNd signatures range from +5.4 to −1.9 in the rhyolites and +6.8 to +2.7 in the basalts, a difference attributable to the absence or presence, respectively, of a significant crustal component. The data and regional tectonic settings of the Avalon and Meguma terranes suggest that the volcanism was generated in three different within-plate settings: (1) Cambrian–early Ordovician volcanism related to thermal decay of late Proterozoic arc magmatism during transtensional deformation; (2) middle Ordovician–early Silurian volcanism during sinistral telescoping between Laurentia and Gondwana where extensional bends in the Appalachians produced rifting; and (3) Devonian volcanism resulting from lithospheric delamination during dextral transpression and telescoping. In each setting, active faults served as conduits for the magmas. Nd isotopic data indicate that the source of the Palaeozoic felsic volcanic rocks is isotopically indistinguishable beneath southern and northern Nova Scotia and did not substantially change with time. This crustal source appears to have separated from the mantle during the Proterozoic, a conclusion consistent with the hypothesis that the Palaeozoic rocks in Nova Scotia were deposited upon a late Proterozoic oceanic–cratonic volcanic arc terrane. The Nd data, when combined with published faunal, palaeomagnetic and U–Pb isotopic data, suggest that the Avalon Terrane was peripheral to Gondwana off northwestern South America during Neoproterozoic and early Palaeozoic times.