Middle Neoproterozoic sedimentary strata are widely distributed on the periphery of the Yangtze Block. In the western Jiangnan Orogen, they are divided into the Lengjiaxi and Banxi groups by the “Wuling unconformity,” and the Banxi Group is further divided into the Madiyi Formation and Wuqiangxi Formation by the “Xihuangshan unconformity.” However, the timing and tectonic significance of the Wuling and Xihuangshan unconformities remain unclear, which hampers our understanding of the Precambrian tectonic evolution of the Yangtze Block. Zircon U–Pb dating and Lu–Hf isotopic analysis were performed on the sedimentary rocks above and below the two unconformity boundaries in the western Jiangnan Orogen. These data were used to trace sedimentary provenance and provide new insights into the basin evolution and tectonic significance of the unconformities. Combined with previous studies, the Wuling unconformity is bracketed to have formed between ~830 and 813 Ma, and the provenance of the sediments above the unconformity remained unchanged. The detrital zircons from the upper parts of the Lengjiaxi Group and lower parts of the Banxi Group show the primary peak ages of 800–1000 Ma, 1.0–1.30 Ga, 1.40–1.90 Ga, and 2.30–2.60 Ga, and the provenance mainly derived from the southwestern margin of the Yangtze Block, Cathaysia Block, and Jiangnan Orogen. The provenance from the Cathaysia Block occurred in the upper part of the Lengjiaxi Group, indicating that the Yangtze Block and Cathaysia Block merged in the western Jiangnan Orogen earlier than the formation time of the Wuling unconformity (~830–813 Ma) and the collisional time in the eastern Jiangnan Orogen (~820–800 Ma). Thus, the collision between the Yangtze and Cathaysia blocks may have undergone a scissor-like closure process from west to east. The formation time of the Xihuangshan unconformity was at ~800–779 Ma. The field contact relationships changed from an angular unconformity to a disconformity and then to conformity, from north to south, indicating that the Xihuangshan unconformity was controlled by tectonic movement in the north. The provenance of the sedimentary strata changed above the Xihuangshan unconformity. The detrital zircon age peaks of the upper Banxi Group are 755–1000 Ma, 1.90–2.10 Ga, and 2.35–2.70 Ga, and the detritus were derived from the northern margin of the Yangtze Block and the Jiangnan Orogen. This unconformity is coeval with that of the ~800–780 Ma collisional orogeny at the northern and northwestern margins of the Yangtze Block. Thus, the Xihuangshan unconformity is likely a response to the collision orogeny in the northern and northwestern margins of the Yangtze Block and induces the transition of sedimentary provenance.