| Summary: | The ozone/peroxymonosulfate (O<sub>3</sub>/PMS) system has attracted widespread attention from researchers owing to its ability to produce hydroxyl radicals (•OH) and sulfate radicals (SO<sub>4</sub><sup>•−</sup>) simultaneously. The existing research has shown that the O<sub>3</sub>/PMS system significantly degrades refinery trace organic compounds (TrOCs) in highly concentrated organic wastewater. However, there is still a lack of systematic understanding of the O<sub>3</sub>/PMS system, which has created a significant loophole in its application in the treatment of highly concentrated organic wastewater. Hence, this paper reviewed the specific degradation effect, toxicity change, reaction mechanism, various influencing factors and the cause of oxidation byproducts (OBPs) of various TrOCs when the O<sub>3</sub>/PMS system is applied to the degradation of highly concentrated organic wastewater. In addition, the effects of different reaction conditions on the O<sub>3</sub>/PMS system were comprehensively evaluated. Furthermore, given the limited understanding of the O<sub>3</sub>/PMS system in the degradation of TrOCs and the formation of OBPs, an outlook on potential future research was presented. Finally, this paper comprehensively evaluated the degradation of TrOCs in highly concentrated organic wastewater by the O<sub>3</sub>/PMS system, filling the gaps in scale research, operation cost, sustainability and overall feasibility.
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