Subvertically- to vertically-dipping Archean strata provide an excellent opportunity to study synvolcanic structures and internal organization of subaqueous volcanic complexes. The Abitibi greenstone belt in Quebec, Canada, hosts a number of these volcanic complexes and specifically the unique Blake River Megacaldera Complex. The Blake River Megacaldera Complex is composed of (i) an initial shield phase known as the Misema Caldera and (ii) two graben-type calderas known as the New Senator and Noranda calderas. The southern portion of the New Senator Caldera, the focus of this study, is of particular interest as the structure hosts the 54 Mt Horne Au-rich volcanogenic massive sulfide deposit. Detailed facies mapping, coupled with geochemical and geochronological analysis at multiple outcrop localities throughout the city of Rouyn-Noranda, Quebec, show that the stratigraphy of the New Senator Caldera is dominated by subaqueous effusive mafic volcanic facies with local felsic effusive and intrusive deposits. With the incorporation of structural data, we have used synvolcanic faults and dyke complexes to divide these facies into specific blocks within this region, here renamed the Rouyn–Pelletier sector. This study focuses on the facies and characteristics of the Pelletier, Senator, and Glenwood blocks and identifies the Évain, Stadacona, and Chadbourne blocks. Geochronological analysis reveals that facies of the Glenwood Block are approximately the same age as those of the felsic flows of the previously identified Horne Block. Together, all extrusive and intrusive volcanic facies from the Stadacona unit north to the Horne Creek fault compose a large caldera complex known as the Rouyn–Pelletier Caldera Complex.