The recognition of unconformities is important for determining the long-term evolution of orogenic belts. We document an unconformity between Tonian and Cryogenian strata of the Nanhua Basin of South China. This stratigraphic break has previously been termed the Xuefeng Movement and is developed within the Yangtze Block and western Cathaysia Block. Deformation characteristics and detrital zircon U-Pb geochronology from rock units underlying and overlying the unconformity (i.e., the Niuguping and Gucheng formations, respectively) from the Anhua region of the northern Hunan Province in the southeastern Yangtze Block are documented. The Niuguping Formation displays a set of top-to-northwest imbricate thrust faults and related fault-propagation folds, NEE-plunging subparallel crenulation lineations, a foliation, and shows widespread greenschist facies metamorphism. In contrast, the overlying Gucheng Formation exhibits no obvious stratal deformation (apart from a mild inclination of bedding) and is unmetamorphosed. Detrital zircon age spectra of the samples from the Niuguping Formation are characterized by unimodal age peaks of ca. 750–730 Ma, while those of the samples from the Gucheng Formation yield a multimodal age distribution, with a few syn-sedimentary detrital zircons (<700 Ma), and much older zircons with age peaks of ca. 800 Ma, 2.1–1.9 Ga, and 2.6–2.3 Ga. Combining this data with previous geochronology indicates deposition of the Niuguping and Gucheng formations in the late Tonian (725–720 Ma) and Cryogenian (690–660 Ma), respectively. The time gap across the unconformity is some 30 Ma (720–690 Ma). The unconformity and associated structural and metamorphic break extend across the Yangtze Block and western Cathaysia Block, defining a major regional orogenic event. The significantly different detrital zircon spectra of strata across the unconformity suggest a dramatic change in the source due to the Xuefeng Orogeny in the Yangtze Block. Zircon U-Pb-Hf isotopic evidence indicates that detritus of the Niuguping Formation below the unconformity was derived from syn-depositional magmatic activity in the northern Yangtze Block, while a significant increase of Archean to Paleoproterozoic ages for the Gucheng Formation, suggests that the Xuefeng Orogeny resulted in crustal thickening and denudation in the northern Yangtze Block. These changes in provenance, along with changing deformational and metamorphic patterns, indicate evolution of the Nanhua Basin from a compressional to an extensional back-arc basin, which we infer is related to tectonic switching from an advancing to a retreating subduction system in the northern Yangtze Block at the time of the unconformity.