<p>In this study, the Cu₇Mn₂ bimetallic cluster was synthesized via a solvothermal method using copper (II) chloride dihydrate (CuCl₂·2H₂O) and manganese (II) chloride tetrahydrate (MnCl₂·4H₂O) as the metal centers, and 1,2-cyclohexanediamine-N,N′-bis-(3-carboxylsalicylide) as the ligand. Subsequently, the Cu₇Mn₂ bimetallic cluster fiber coating was prepared using a physical coating method and applied for the solid phase microextraction (SPME) of 7 polycyclic aromatic hydrocarbons (PAHs). The coating was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis, and contact angle measurement. Based on adsorption isotherms and density functional theory (DFT) calculation, the adsorption mechanism was speculated to be hydrophobic interaction, π-π stacking, and N − H···π interaction. The coating exhibited higher extraction efficiency for 7 PAHs than the Cu cluster, Mn cluster, commercial PDMS, and PDMS/CAR fiber coatings. Under the optimized extraction conditions, an SPME-HPLC method was developed for the determination of 7 PAHs in corn oil, sesame oil, blended oil, and rapeseed oil. The linear ranges of the method were 1.0 − 1000&#xa0;µg·kg^–1 for naphthalene, 0.1 − 1000&#xa0;µg·kg^–1 for anthracene, phenanthrene, and pyrene, 3.0 − 1000&#xa0;µg·kg^–1 for fluorene, 0.3 − 1000&#xa0;µg·kg^–1 for fluoranthene, and 1.5 − 1000&#xa0;µg·kg^–1 for 1-methylnaphthalene (<i>R</i>² &gt; 0.99), respectively. The limits of detection (LODs, S/N = 3) and the limits of quantitation (LOQs, S/N = 10) were in the ranges of 0.030 − 1.0&#xa0;µg·kg^–1 and 0.10 − 3.0&#xa0;µg·kg^–1, respectively. The precisions (RSDs) were less than 10.0% and the recoveries were in the range of 82.9 − 115.2%. These results demonstrate that the Cu₇Mn₂ bimetallic cluster coating is an effective SPME adsorbent for separation and sensitive determination of PAHs in edible oils.</p> Graphical Abstract <p></p>