Single-atom catalysts (SACs) have gained widespread popularity in heterogeneous catalyzed-advanced oxidation processes (AOPs), owing to their optimal metal atom utilization efficiency and excellent recyclability by triggering reactive oxidative species (ROS) for target pollutant oxidation in water. Systematic summaries regarding the correlation between the active sites, catalytic activity, and reactive species of SACs have rarely been reported. This review provides an overview of the catalytic performance of carbon- and metal oxide-supported SACs in Fenton-like reactions, as well as the different oxidation pathways induced by the metal and non-metal active sites, including radical-based pathways (e.g. •OH and SO4•-) and nonradical-based pathways (e.g. 1O2, high-valent metal-oxo species, and direct electron transfer). Thereafter, we discussed the effects of metal types, coordination environments, and spin states on the overall catalytic performance and the generated ROS in Fenton-like reactions. Additionally, we provide a perspective on the future challenges and prospects for SACs in water purification.