The Darriwilian (Middle Ordovician) is marked by a striking peak of the Great Ordovician Biodiversification Event (GOBE) followed by an abrupt ∼50 % decline in invertebrate species. Understanding the ultimate driving mechanism behind this biotic turnover and its correlation with those proximate climatic-oceanic changes that directly result in elevated biotic mortality have garnered considerable attention. One hypothesis posits that oceanic redox evolution actively influenced biodiversification, and progressive expansion of marine anoxia caused the termination of this biotic event. In this study, we present sedimentological and geochemical profiles for three outcrops of different lithofacies across the Middle-Upper Ordovician transition, ranging from carbonate platform to deep-water slope-basinal facies of the Tarim and South China cratons. Mercury isotopes reveal that recurrent and spatially dynamic photic-zone euxinia (PZE) occurred in the slope-basinal facies while being absent in platform facies. Mass balance model results suggest that ∼23 % of local atmospheric Hg was sequestered in marine sediments due to elevated dissolved H₂S in surface waters. This finding suggests that destabilized oceanic redox conditions developed during climatic cooling, particularly shoaling and upwelling of deep-marine euxinic waters into the photic zone, coupled with global carbon-cycle disturbances, resulted in biodiversity decline following the peak of the GOBE.