The early Cambrian was an important interval in Earth history, marked by significant evolution of both life and the marine environments it inhabited. While enhanced hydrothermal activity has been proposed as a trigger for ecosystem perturbations in the early Cambrian, it remains unclear how intense and how long such perturbations may have been. To address this, we examined mercury (Hg) concentrations and mercury isotopes, as well as major and trace elements, of organic-rich black shales of the lower Cambrian Niutitang Formation, in the Tongren area of Guizhou Province, South China. Our data show that Hg in these sediments is hosted dominantly by organic matter. Elevated raw and normalized Hg contents provide direct evidence of intense hydrothermal activity during the early Cambrian in South China. We suggest that high metal flux (e.g., Mo, U, and Ba) into the seawater occurred through this intense submarine volcanism, altering seawater compositions. Intense hydrothermal activity was likely a significant trigger of environmental and biological evolution during the early Cambrian in South China.