A novel solid-phase microextraction (SPME) fiber for extraction of polar aromatic compounds was prepared by chemically bonding a dextran/graphene oxide (GO) composite material on stainless steel wire. Coupled with gas chromatography (GC), the fiber was used to extract phenols and halogenated aromatic compounds in aqueous samples. The analytical performances of the proposed fiber were evaluated under optimized extraction conditions. The wide linear ranges were 0.10–200 μg L⁻¹, 0.20–200 μg L⁻¹ for different target compounds; the detection limits ranged from 0.015 μg L⁻¹ to 0.050 μg L⁻¹; single-fiber repeatability and fiber-to-fiber reproducibility were in the range of 2.7–10.6% and 5.5–13.7%, respectively. The outstanding stability of the prepared fiber was demonstrated by its ability to sustain more than 100 times usage with relative standard deviations for extraction efficiency less than 13.7%. The dextran/GO-coated SPME fiber was applied to determine phenols and halogenated aromatics in two real water samples, and satisfactory results were obtained.