The Ordovician-Silurian (O-S) transition coincided with significant environmental and biological changes. In South China, the Yangtze Platform experienced both global and regional events at this time, including sea-level fluctuations, tectonic movements, volcanic eruptions, mass extinction, and widespread anoxia. The O-S transitional strata of the Yangtze Platform comprise organic-rich black shales that are an important oil source rock. To explore the evolution of watermass chemistry and its relationship to organic matter accumulation, we conducted an integrated Fe-S-C geochemical study (i.e., Fe-speciation, δ 13 C org , δ 34 S py , pyrite-S and TOC) of the O-S boundary sections at Datianba (Chongqing Municipality) and Shuanghe (Sichuan Province). These sections were located in the restricted inner Yangtze Sea, in contrast to the previously studied Wangjiawan section, which was deposited in a more open setting of the outer Yangtze Sea. In contrast to the well-oxygenated conditions at Wangjiawan, the Datianba and Shuanghe sections record persistently anoxic, and episodically euxinic, conditions during the Hirnantian, which can be explained by the unique paleogeography and restricted hydrography of the inner Yangtze Sea. We propose that the regional Kwangsian Orogeny, which was driven by collision of the Yangtze and Cathaysia blocks, played a key role in basin development, watermass chemistry changes, and accumulation of Wufeng Formation black shales within the Yangtze Sea. The more widespread black shales of the Lower Silurian Lungmachi Formation were linked to the post-Hirnantian global marine transgression.