<p> A Cu₇Mn₂ bimetallic cluster (Cu₇Mn₂) fiber coating was prepared for headspace solid-phase microextraction (HS-SPME) of 10 phenolic compounds. The fiber coating was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, nitrogen adsorption–desorption measurement, and thermogravimetric analysis. The adsorption performance was investigated via adsorption isotherm experiments. The results indicated that the adsorption of the Cu₇Mn₂ fiber coating for 10 phenolic compounds followed the Freundlich isotherm model, suggesting multilayer adsorption. Density functional theory (DFT) calculations revealed that the adsorption mechanism primarily involves hydrogen bonding, π − π stacking and hydrophobic interactions. After the extraction conditions were optimized, an HS-SPME-GC-FID method was established for the determination of 10 phenolic compounds in environmental water samples. The linear ranges were 0.003−500&#xa0;μg·L⁻¹ for 2-NP, 0.009–500&#xa0;μg·L⁻¹ for 2-CP, 0.015–500&#xa0;μg·L⁻¹ for 2,4-DCP and 2,6-DCP, 0.030–500&#xa0;μg·L⁻¹ for 2,4-DMP, 0.050–500&#xa0;μg·L⁻¹ for PTBP, 0.100–500&#xa0;μg·L⁻¹ for phenol and 3-MP, and 0.150–500&#xa0;μg·L⁻¹ for 2-MP and 4-CP (<i>R</i>² ≥ 0.9908). The limits of detection (LODs, S/N=3) were 0.001−0.045&#xa0;μg·L⁻¹. The recoveries of 10 phenolic compounds in water samples ranged from 80.2% to 119.8%. The enrichment factors ranged from 303 to 3435, and the coating could be reused at least 120 times. The established HS-SPME-GC-FID method is reliable for the determination of 10 phenolic compounds in real water samples.</p> Graphical Abstract <p></p>