Phenol is a common pollutant in various wastewater, which is required to be removed to a certain standard before the wastewater can be discharged. Persulfate-based advanced oxidation processes (PS-AOPs) are an effective technology for phenol removal, with efficacy contingent upon the activation methods and materials employed. In this study, Fe-based metal-organic frameworks (Fe-MOFs) constructed with carboxylic acid as a ligand were synthesized by a solvothermal method, which can form chelates with ferrous ions. Fe-MOFs showed the activity similar to the homogeneous catalyst thus improving their activation efficiency, and can be used to activate peroxymonosulfate (PMS) for phenol degradation in water. The effects of catalyst dosage, PMS and phenol concentration, temperature, and pH on the degradation efficiency were investigated. Under the optimum reaction conditions, the 96 % of phenol can be rapidly removed in 5 min. SO4·− was determined as the primary radical. Fe species on Fe-MOFs acted as the key active sites. Density functional theory (DFT) analysis suggested enhanced charge redistribution, fostering electron-rich sites that facilitate electron transfer in AOPs, thus boosting phenol degradation. The Fe-MOFs/PMS system enables iron recycling and efficient phenol degradation in water, indicating the potential for phenol-contaminated water treatment.