Abstract: A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) and a preparation method and an application thereof are provided. According to the method, a PMS activator ZSM-5-(C@Fe) with a millimeter-scale stable structure is synthesized in the following steps: (1) preprocessing a ZSM-5 by a carboxylation method to obtain a ZSM-5-COOH; (2) synthesizing a ferrous metal organic framework material by a thermal method to obtain a precursor Fe (II)-MOF-74; (3) dispersing the ZSM-5-COOH in the step (1) and an ethyldiol methacrylate in an acetonitrile, and mixing evenly to obtain a mixed solution; and adding the precursor Fe(II)-MOF-74 in the step (2) into the mixed solution, carrying out a stirring reaction under an action of an initiator, filtering to obtain a precipitate, washing, and drying in vacuum to obtain ZSM-5-MOFs; and (4) in a nitrogen atmosphere, heating the ZSM-5-MOFs in the step (3) to carry out high-temperature pyrolysis to obtain the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe).