The Central Gneiss Belt, southwestern Grenville Province, is characterized by parautochthonous crust in the north and allochthonous lithotectonic domains in the south. Despite nearly two decades of study, the basal décollement to allochthonous domains transported from the southeast, known as the allochthon boundary thrust, has not been precisely located throughout much of the belt. Between Lake Nipissing and Georgian Bay where its surface trace is known, it separates 1.24 Ga Sudbury metadiabase in the footwall from eclogite remnants and 1.17–1.15 Ga coronitic olivine metagabbro confined to its hanging wall. On the premise that this relationship can be used to trace the allochthon boundary thrust elsewhere in the Central Gneiss Belt, we have sought to extend the known distribution of these mafic rock types, making use of field, petrographic, and geochemical criteria to identify them. New occurrences of all three mafic types are identified in a region extending from south of Lake Nipissing to western Quebec, and the mutually exclusive pattern of occurrence is maintained within this region. Structural trends and reconnaissance mapping of high-strain zones that appear to represent a structural barrier to the mafic suites suggest that the allochthon boundary thrust lies well to the north of its previously suggested location. Our preferred surface trace for it passes around the southern end of the Powassan batholith and through the town of North Bay before turning east to join up with the Lac Watson shear zone in western Quebec. This suggests that a large segment of “parautochthonous” crust lying north of, and including, the Algonquin domain is in fact allochthonous. The mutually exclusive distribution of the mafic suites points to significant separation of allochthonous and parautochthonous components prior to the Grenvillian orogeny, in accord with models of pre-Grenvillian continental rifting proposed by others. Despite a relative abundance of geological and geochronological data for the Central Gneiss Belt and a mafic rock distribution that appears to successfully locate a major tectonic boundary, we emphasize the need for additional field and laboratory work aimed at testing our structural model.