An easy method to prepare solid phase microextraction fibers by introducing an inorganic binder was demonstrated in this study, where MoS₂ was selected as the extraction phase material because of its graphite-like layered structure with large specific adsorption area and good stability, and was then adhered to a stainless steel wire by acid aluminum phosphate binder with the spraying method. The as-prepared solid phase microextraction fiber coupled with gas chromatography was then used to extract some polycyclic aromatic hydrocarbons target analytes including the low-volatile benzo(a)pyrene etc. from a standard sample. Comparing with the MoS₂-epoxy resin and commercial polyacrylate fibers, the MoS₂-acid aluminum phosphate fiber has a higher thermal stability because of highly thermal stable acid aluminum phosphate, which is durable for a long service life at a high temperature (320 °C), and has the advantage in the extraction of low-volatility analytes. After the optimization of adsorption and desorption factors (ionic strength, adsorption time and temperature, and desorption temperature), method detection limits of <0.1 μg L⁻¹ were achieved, and the calibration curves were all linear (R² ≥ 0.9981) within the range of 0.1–100 μg L⁻¹. The satisfying repeatability was also achieved, the RSD values of single-fiber were 3.49–5.81%, and the ones of fiber-to-fiber were 5.32–7.22%. As a result, the present fiber with good thermal stability can work at high temperature for a long service life, which is useful for the detection of low-volatility target analytes in practical applications.