The Boil Mountain ophiolite complex of west-central Maine is widely interpreted to mark the Lower Ordovician Penobscottian suture between the Dunnage, Chain Lakes, and Gander terranes. The ophiolite consists of two distinct volcanic groups, including a lower island-arc tholeiite sequence and an upper mid-ocean-ridge basalt sequence. A new Middle Ordovician 477 ± 1 Ma U–Pb age on a tonalite sill that intrudes the lower volcanic–gabbroic sequence is younger than other ca. 500 Ma age constraints for the ophiolite and represents a maximum age for the ophiolite prior to final emplacement over gneissic rocks of the Chain Lakes massif. A comparison of ages and paleogeography of the Boil Mountain ophiolite with ophiolitic sequences in Quebec and Newfoundland indicates that the Taconian and Penobscottian orogenies and ophiolite obduction occurred simultaneously, although on different margins of the Iapetus Ocean. The Taconian ophiolite sequences were obducted onto the Appalachian margin of Laurentia during its collision with the Notre Dame – Bronson Hill belt in the Middle Ordovician, whereas the Boil Mountain ophiolite was obducted onto the Gander margin of Gondwana during its collision with the Exploits subzone – Penobscot arc of the Dunnage terrane in the Lower – Middle Ordovician. We suggest that the lower volcanic–gabbroic sequence of the Boil Mountain ophiolite represents the fore-arc ophiolitic basement to the Penobscot arc. Middle Ordovician rifting of the Penobscottian orogenic collage on the Gander margin formed a new volcanic sequence (Popelogan arc) in front of a growing back-arc basin, and erupted the upper tholeiitic sequence of the Boil Mountain ophiolite in a back-arc-basin setting. The tonalité sill formed during this event by partial melting of the lower volcanic–gabbroic sequence. Spreading in this back-arc basin (Tetagouche basin) brought a fragment of the Gander margin (Chain Lakes massif), along with an allochthonous ophiolitic cover (Boil Mountain complex) across Iapetus, where it collided with the Taconic modified margin of North America in the Late Ordovician and was then intruded by the Ashgillian Attean pluton.