Mercury (Hg) anomalies in sedimentary records are a newly developed proxy of large volcanism in the geological past. Tuff layers host abundant volcanic ash and record key information on the type of volcanic emission (e.g., arc volcanism and large igneous province eruptions). Here, we measured the Hg isotopic compositions of several tuff layers in South China. Tuff samples in the Late Ordovician Wufeng Formation and the Middle Triassic Guanling Formation mostly show positive Δ¹⁹⁹Hg values of – 0.01 to 0.10‰ and – 0.06 to 0.16‰, respectively, suggesting arc volcanism occurred during these two periods. Tuff samples in the Middle Permian Dachang Layer mostly show near-zero Δ¹⁹⁹Hg values (– 0.08 to 0.00‰), suggesting volcanism was driven by the Emeishan large igneous province eruption. Results of this study verify Hg isotopes as a useful proxy in revealing the type of volcanism in geological history.