In this paper, the potential applications of metal–organic framework (MOF) materials as fiber coatings for the solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs) in water samples were explored. Fibers coated with MIL-53(Al, Cr, Fe) materials were fabricated by an adhesive method for SPME. The quantitation was performed by gas chromatography–tandem mass spectrometry (GC–MS/MS) using the multiple reaction monitoring mode. Among the three MIL-53(M) coatings, MIL-53(Al) showed the highest extraction efficiency towards PAHs under the current fabrication procedure. Under optimized conditions, the MIL-53(Al)-coated fiber showed good precision (relative standard deviation <12.5%), low detection limits (0.10 ng L⁻¹ to 0.73 ng L⁻¹, S/N = 3), and good linearity (R² > 0.98) for aqueous solutions containing 16 PAH . The fiber also offered high thermal and chemical stability. The method developed based on MIL-53(Al) SPME–GC–MS/MS was successfully applied in the analysis of real water samples. Based on the simulation results, the PAHs were adsorbed on MIL-53(Al) primarily through the hydrophobic and π–π interactions between PAHs and the organic linker of the material. The results presented in this paper indicate that water-stable MOF materials have great potential for the SPME of aromatic compounds in water samples.