To improve understanding of the environmental influential and controlling factors of the Great Ordovician Biodiversification Event (GOBE), total organic carbon content (TOC), total sulfur content (TS), and sulfur isotope of pyrite (δ34Spy) of black shale of the Jiangjunling section, in southern Anhui Province, China are analyzed. TOC and TS show positive correlation, indicating non-euxinic environment. δ34Spy exhibits obvious decrease in Floian and more oscillation in the Middle Ordovician. Combined with global sulfur isotope of carbonate-associated sulfate (δ34SCAS) and δ34Spy data from previous researches, a marine oxygenation event is suggested by decreasing pyrite burial and increasing sulfur isotopic fractionation during the latest Tremadocian to middle Floian, which might boost GOBE. During the late Floian to Darriwilian, δ34SCAS from different areas decreases in succession, while δ34Spy is characterized by large oscillation, which is contributed to low sulfate concentration and sulfide reoxidation in the ocean.