A covalent organic framework modified graphitic carbon nitride ([email protected]) was synthesized by modifying the graphitic carbon nitride (g-C3N4) with a covalent organic framework (COF-TpBD). The synthesis conditions including the mass ratio between g-C3N4 and benzidine (BD), solvent type, reaction temperature and reaction time were optimized. Under the optimal synthetic conditions, a novel spiny dendritic [email protected] adsorbent was obtained. The [email protected] was then coated on stainless-steel wire by sol-gel technique and the coated fiber was used for the solid phase microextraction of polycyclic aromatic hydrocarbons prior to gas chromatography-mass spectrometric detection. The established method was successfully applied to determine eight PAHs in six environmental water samples. Under the optimal extraction conditions, a wide linear quantification range for the analytes was obtained from 0.07 to 60.0 ng mL-1 with the coefficients of determination varying from 0.9979 to 0.9998, and the limits of detection (S/N = 3) ranged from 0.02 to 0.05 ng mL-1. The relative recoveries of the analytes for the six environmental water samples at the spiked concentrations of 0.2, 0.5, 3.0 and 30.0 ng mL-1 were between 83.6% and 118% with the relative standard deviations ranging from 2.4% to 11.3%. Copyright © 2020. Published by Elsevier B.V.