A novel MIL-88-NH2@COF composite was produced by in situ growth of covalent organic framework (COF) on the metal-organic framework (MOF) surface. To obtain a coating fiber for solid-phase microextraction (SPME), the MIL-88-NH2@COF composite physically adhered to the stainless steel wire. Combined with gas chromatography-flame ionization detection (GC-FID), various analytes such as chlorophenols (CPs), phthalates (PAEs), and polycyclic aromatic hydrocarbons (PAHs) were extracted and determined to evaluate the extraction performance of MIL-88-NH2@COF coated fibers and explore their extraction mechanism. This composite exhibit excellent extraction performance and adsorption capacity for various analytes, especially for PAHs with enrichment factor up to 9858. The SPME-GC-FID method based on MIL-88-NH2@COF fiber was established for the determination of five PAHs after the main extraction conditions were optimized. Under optimal conditions, the proposed technique showed a wide linear range (1-150ngmL-1) with a low limit of detection (0.019ngmL-1) and a high coefficient of determination (R2 > 0.99). The developed SPME-GC-FID method was used to determine PAHs in green tea and black tea samples, with good recoveries of 51.70-103.64% and 68.56-103.64%, respectively. It is worth mentioning that this is the first time MIL-88-NH2@COF composites have been prepared and applied to SPME. The preparation method of the composite provides a new idea in adsorbent preparation, which will contribute to the field of SPME.