The Newfoundland Appalachians are a classic area for studying the record of arc development and terrane accretion processes with excellent exposure to different crustal levels that are minimally deformed and metamorphosed. This area also provides a link between the once continuous Appalachian and Caledonian orogens. The Annieopsquotch Accretionary Tract lies along the Red Indian Line, within the peri-Laurentian realm of the central Newfoundland Appalachians. The Darriwilian (468–461 Ma) tectonostratigraphic units of the Annieopsquotch Accretionary Tract are commonly characterized by polymictic volcanogenic conglomerate horizons. A conglomerate horizon at the interface between a suprasubduction zone ophiolite and its calc-alkaline volcanic arc cover sequence is herein investigated for zircon and geochemical provenance. Geochronology revealed a maximum age of deposition of 467 ± 4 Ma with zircon inheritance ranging from ca. 500 to 2800 Ma, consistent with a peri-Laurentian continental basement source. Four types of volcanogenic conglomerate clasts are noted on the basis of lithogeochemistry: arc andesite; calc-alkaline basalt; tholeiitic basalt; and non-arc rhyodacite. Tholeiitic basalt clasts are likely locally derived, perhaps from the underlying Skidder Formation. Other volcanic clasts do not have any known geochemical equivalents in the Annieopsquotch Accretionary Tract and hence appear to be exotic. The dominant zircon population suggests that the exotic clasts were derived from a ca. 467 Ma peri-Laurentian andesitic volcanic arc that once formed part of the Annieopsquotch Accretionary Tract.