The aromatic organic compounds present in groundwater environments have low contents, high toxicity, long half-lives and stable chemical properties, which increase the difficulty of degradation under natural conditions. In this study, an zero-valent iron activated peroxymonosulfate system (Fe0/PMS) was constructed to remove common aromatic organic compounds in groundwater. The results showed that at an initial pH of 7.0, Fe0=0.3 g/L, PMS= 0.5 mM, and initial concentration of organic matter (C0) =0.1 mM, the removal efficiency of the seven aromatic organic compounds by the Fe0/PMS system reached more than 70 %, which shows good removal ability. Alcohol quenching tests and liquid chromatography time-of-flight mass spectrometry tests showed that the main active oxygen species in the system were SO4•─ and OH•, which could efficiently degrade aromatic organic compounds through electrophilic substitution, hydroxylation, carbonylation and decarboxylation reactions and reduce the biological toxicity of organic compounds in wastewater to a certain extent. In the long-term dynamic reaction process, the removal rate of aromatic organic compounds in actual groundwater by the Fe0/PMS system can be maintained above 75 %, and the complex structure can be effectively destroyed. This research can provide a theoretical basis for the efficient treatment of aromatic organic compounds in groundwater.