The Mount Pleasant granite-related polymetallic deposit, located on the southwestern margin of the Late Devonian to Early Carboniferous Mount Pleasant Caldera Complex in southwestern New Brunswick, contains a significant resource of tin, tungsten, molybdenum, zinc, indium, and bismuth. The Caldera Complex comprises Intracaldera, Exocaldera, and Late Caldera-Fill sequences and associated subvolcanic granitic rocks. Three granitic phases of the Mount Pleasant Granitic Suite (Granite I, II, and III) are recognized in the vicinity of the Mount Pleasant deposit and are interpreted to be fractionates of the more regionally exposed McDougall Brook Granitic Suite. Granite I and Granite II are associated with tungsten-molybdenum-bismuth, and tin-zinc-indium mineralization, respectively. Despite extensive research within the Caldera Complex, the exact age of mineralization at Mount Pleasant has never been firmly established. An inferred age of 363 ± 2 Ma was based on the proposed synchronicity of the U-Pb dated Bailey Rock Rhyolite of the Exocaldera Sequence with that of the undated McDougall Brook Granitic Suite, which intrudes the Intracaldera Sequence. Here, we present Re-Os dating of two molybdenite samples associated with the tungsten mineralization related to Granite I at the Fire Tower Zone, that constrain the initial onset of mineralization at Mount Pleasant to be between 369.7±1.6 Ma and 370.1±1.7 Ma. The new Re-Os ages clearly indicate that the McDougall Brook Granitic Suite, which pre-dates mineralization, must be at least seven million years older than the Bailey Rock Rhyolite, whose type-section is located within the Exocaldera Sequence. A re-examination of the gradational relationship between the McDougall Brook Granitic Suite and purported rocks of Bailey Rock Rhyolite within the Intracaldera Sequence revealed that the latter should instead be assigned to the Seelys Formation. Thus, deposition of the polymetallic mineralization likely took place contemporaneously with caldera collapse and an early phase of resurgent doming in response to degassing of the magma chamber rather than being coincident with erosion of the volcanic edifice as inferred from previous modeling of the eruptive history at Mount Pleasant.