The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.