New Re–Os molybdenite geochronology is presented from the Ballachulish Igneous Complex (433.5 ± 1.8 Ma) and the Kilmelford Igneous Complex (425.8 ± 1.7 Ma) of the SW Scottish Highlands. The sulphide mineralization in the Ballachulish Igneous Complex is related to the latest phase of granite magmatism, and therefore the new Re–Os age provides a minimum crystallization age, c. 3.7 Ma earlier than previous crystallization age estimates. This Re–Os age overlaps U–Pb ages obtained from subduction-related granitic and appinitic magmatism north of the Great Glen Fault, and an origin related to active subduction rather than slab breakoff is proposed for the Ballachulish Igneous Complex. Molybdenite mineralization in the Kilmelford Igneous Complex is spatially and genetically associated with porphyry Cu mineralization, which is consistent with the rapid ascent of volatile-rich magma during early rebound following the breakoff of subducted oceanic lithosphere. The Kilmelford Igneous Complex and the coeval Lorn Lava Pile may represent the earliest of the igneous bodies predicted by slab breakoff, indicating that slab breakoff occurred at c. 426 Ma.