Arc-continent collision, followed by subduction polarity flip, occurs during closure of oceanic basins and contributes to the growth of continental crust. Such a setting may lead to a highly unusual association of ultrapotassic and mid-ocean ridge basalt (MORB)-type volcanic rocks as documented here from an Ordovician succession of the Scandinavian Caledonides. Interbedded with deep-marine turbidites, pillow basalts evolve from depleted-MORB (εNdt 9.4) to enriched-MORB (εNdt 4.8) stratigraphically upward, reflecting increasingly deeper melting of asthenospheric mantle. Intercalated intermediate to felsic lava and pyroclastic units, dated at ca. 474−469 Ma, are extremely enriched in incompatible trace elements (e.g., Th) and have low εNdt (−8.0 to −6.6) and high Sri (0.7089−0.7175). These are interpreted as ultrapotassic magmas derived from lithospheric mantle domains metasomatized by late Paleoproterozoic to Neoproterozoic crust-derived material (isotopic model ages 1.7−1.3 Ga). Detrital zircon spectra reveal a composite source for the interbedded turbidites, including Archean, Paleo-, to Neoproterozoic, and Cambro-Ordovician elements; clasts of Hølonda Porphyrite provide a link to the Hølonda terrane of Laurentian affinity. The entire volcano-sedimentary succession is interpreted to have formed in a rift basin that opened along the Laurentian margin as a result of slab rollback subsequent to arc-continent collision, ophiolite obduction and subduction polarity flip. The association of MORBs and ultrapotassic rocks is apparently a unique feature along the Caledonian-Appalachian orogen. Near-analogous modern settings include northern Taiwan and the Tyrrhenian region of the Mediterranean, but other examples of strictly concurrent MORB and ultrapotassic volcanism remain to be documented.