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• Diatomite and CoFe 2 O 4 was effectively assembled to activate peroxymonosulfate. • CoFe 2 O 4 /diatomite catalyst has lower metal dissolution rate. • Surface structure and crystallization dispersion improve activation performance. • The 1O 2 was the primary active substance for BPA degradation. • Weak basic condition enhanced PMS activation and increased BPA degradation. Porous magnetic CoFe 2 O 4 /diatomite catalyst (CFD) was rationally synthesized via a facile citrate combustion process. The relationship between catalytic performance and material properties of the prepared catalysts was comprehensively investigated by various characterizations, especially for the interface interaction between CoFe 2 O 4 and diatomite as well as crystallization regulation of CoFe 2 O 4. Overall, higher specific surface area, overspreading surface hydroxyl groups, better crystal dispersion and abundant surface-active sites make CFD have better degradation performance of bisphenol A (BPA) than pure CoFe 2 O 4 in the presence of peroxymonosulfate (PMS), and the pseudo-first-order reaction rate constant of 40-CFD (40% CoFe 2 O 4 /diatomite) is almost 5.32 times higher than that of pure CoFe 2 O 4. Besides, CFD has excellent magnetic properties, lower metal dissolution rate and good reusability. In addition, electron paramagnetic resonance (EPR) and radical quenching experiments show that sulfate radicals (SO 4 −) and singlet oxygen radicals (1O 2) generated from the electron transfer of BPA molecule and valence state change of transition metals should be the predominant oxidation species. Moreover, possible degradation pathways of BPA are determined by the detection of intermediates derived from the results of liquid chromatograph–mass spectrometer (LC–MS). In brief, it is indicated that the CoFe 2 O 4 /diatomite composite material is an efficient and environmentally friendly catalyst, which has a great potential application in wastewater treatment by activating PMS. [ABSTRACT FROM AUTHOR]