Central Cape Breton Island in Nova Scotia, Canada, is host to ∼700–630 Ma felsic and associated mafic volcanic rocks that are relatively rare in other parts of the Avalon Composite Terrane, occurring elsewhere only in the Stirling Block of southern Cape Breton Island and in parts of eastern Newfoundland. The mafic rocks of central Cape Breton Island are typically intraplate tholeiitic basalts generated by melting of a garnet-bearing mantle source. They lack a continental trace element and εNd imprint although they were emplaced on continental crust; they resemble oceanic island basalts. Contemporaneous volcanism in the Stirling Block is calc-alkaline and formed in a volcanic arc setting. In the absence of evidence for an intervening trench complex or suture, it may be inferred that the central Cape Breton tholeiites formed in a back-arc setting relative to the Stirling Block. This rifting may represent the initial stages of separation of an Avalonian arc from western Gondwana. The arc rifted further between ∼630–610 Ma when the younger Antigonish-Cobequid back-arc basin formed. Subsequently, the extensional arc became convergent, telescoping the back-arc basin. Northwestward migration of calc-alkaline arc magmatism may be related to shallowing of the associated Benioff zone through time.