Several variably deformed and metamorphosed, late Precambrian volcanic–sedimentary successions have been recognized within the Avalon composite terrane exposed in the Caledonian Highlands of southern New Brunswick. Whole-rock samples of metasedimentary phyllite and phyllitic metatuff from the oldest (ca. 600–635 Ma) Avalonian succession display similar, internally discordant 40Ar/39Ar age and apparent K/Ca spectra. Intermediate-temperature gas fractions were experimentally evolved solely from very fine grained, cleavage-aligned white micas. These yield apparent ages between ca. 430 and 410 Ma, and are interpreted to closely date a static Late Silurian – Early Devonian thermal rejuvenation.Evidence for a Silurian – Devonian thermal event has not been previously documented in Avalonian rocks of the Caledonian Highlands (Caledonia assemblage). However, a thermal overprint of similar age (ca. 400 Ma) is recorded by metamorphic muscovite in high-grade gneisses and platformal metasedimentary rocks (Brookville assemblage), which are in tectonic contact with the low-grade Caledonia assemblage. These potentially correlative thermal overprints may provide minimum age constraints on the juxtaposition of these contrasting tectono-stratigraphic assemblages, which are likely to have been palinspastically separate tectonic elements during the earliest Paleozoic.