New stratigraphic, geochemical, and geochronological data from the late Paleozoic depositional record in Anhui Province, China, signal the onset of active-margin magmatism in East Asia. Chert-shale sequences of the Gufeng Formation are part of a Carboniferous–Permian carbonate platform that developed along the passive margin of the South China block. Thin tuffaceous interlayers in these sequences represent distal ash deposits, marking discrete volcanic events. Sensitive high-resolution ion microprobe (SHRIMP) U-Pb zircon dating of the stratigraphically bottom and near-top tuffaceous interlayers has revealed crystallization ages of 270 Ma and 264 Ma, respectively, constraining the time span of subaerial eruptions to ∼6 m.y. during the Guadalupian Epoch. High SiO2 and Al2O3 contents, enrichments in large ion lithophile and light rare earth elements, and depletion patterns of high field strength and heavy rare earth elements indicate a calc-alkaline magma source in an arc setting for the origin of these volcanic tuff deposits. Detrital zircon geochronology of sandstones in the overlying Longtan Formation shows two prominent age populations of 290–250 Ma and 1910–1800 Ma. The former age cluster overlaps with the tightly constrained zircon ages obtained from the Gufeng Formation. The latter age group is compatible with the known magmatic-metamorphic ages from Cathaysia in the South China block, and it points to the existence of a NE-SW–trending topographic high as a major sediment source. We interpret this topographic high and silicic volcanism to represent an Andean-type active margin, developed above a north-dipping paleo-Pacific slab. Our tightly constrained Guadalupian eruption ages indicate the inception of magmatic arc construction and mark a major switch from passive- to active-margin tectonics along SE Asia.