Biotic extinction during the Guadalupian-Lopingian (G-L) transition is actively debated, with its timing, validity, and causality all questioned. Here, we show, based on detailed sedimentary, paleoecologic, and geochemical analyses of the Penglaitan section in South China, that this intra-Permian biotic crisis began with the demise of a metazoan reef system and extinction of corals and alatoconchid bivalves in the late Guadalupian. A second crisis, among nektonic organisms, occurred around the G-L boundary. Mercury concentration/total organic carbon (Hg/TOC) ratios show two anomalies. The first Hg/TOC peak broadly coincides with the reef collapse and a positive shift in Δ199Hg values during a lowstand interval, which was followed by microbial proliferation. A larger Hg/TOC peak is found just above the G-L boundary and speculatively represents a main eruption episode of the Emeishan large igneous province (ELIP). This volatile volcanism coincided with nektonic extinction, a negative δ13Ccarb excursion, anoxia, and sea-level rise. The temporal coincidence of these phenomena supports a cause-and-effect relationship and indicates that the eruption of the ELIP likely triggered the G-L crisis.