Core-shell structured Fe2O3/CeO2@MnO2 microspheres were fabricated and used as solid-phase microextraction coating for determination of polycyclic aromatic hydrocarbons (PAHs) in water samples. XPS spectra demonstrated the generation of abundant surface oxygen on Fe2O3/CeO2@MnO2 microspheres, which provided binding sites for enhancement of analyte extraction. Under optimized conditions, the proposed method presented good linearity in the concentration range 0.04–100 ng mL−1, with low limits of detection varying from 0.38 to 3.57 ng L−1 for eight PAHs. Relative standard deviations for a single fiber and five batches of fibers were in the ranges of 4.1–8.2% and 7.1–11.4%, respectively. The proposed method was successfully used for determination of PAHs in real river water samples with recoveries ranging from 87.1 to 115.9%. The proposed method using as-prepared Fe2O3/CeO2@MnO2 microspheres as SPME coating exhibit significant potential for real sample analysis due to its excellent reproducibility, high sensitivity, and good linearity. [ABSTRACT FROM AUTHOR]