The　efficient　enrichment　of　trace　polybrominated　diphenyl　ethers　(PBDEs)　in　environmental　waters　remains　challenging　for　environmental　monitoring　and　analysis.　Herein,　a　covalent　organic　frameworks-poly(ionic　liquid)s　hybrid　material　(COF-γ-PIL)　is　synthesized　by　threading　poly(1-vinyl-3-methylimidazolium　bis　((trifluoromethyl)　sulfonyl)　imide)　into　a　vinyl-decorated　COF　via　photopolymerization.　The　resultant　hybrid　retains　the　crystallinity　and　porosity　of　COF,　thus　offering　adequate　adsorption　sites　for　the　targets.　PIL　threaded　in　COF　facilitates　the　synergistic　capture　of　target　molecules　within　the　hybrid　through　multiple　interactions,　including　Van　der　Waals　forces,　weak　hydrogen　bonding,　and　hydrophobic　interactions.　As　a　proof　of　concept,　COF-γ-PIL　was　utilized　as　the　fiber　coating　for　SPME　of　PBDEs　in　waters　prior　to　their　analysis　via　GC-MS.　Excellent　analytical　results　were　achieved,　with　wide　linearity　(0.01–100　ng　L−1),　low　limits　of　detection　(0.0021–0.014　ng　L−1),　and　satisfactory　recoveries　(78.6%−103.6%).　The　outstanding　extraction　performance　can　be　ascribed　to　the　extraordinary　flexibility　of　the　active　fraction　on　linear　polymers　threaded　in　COF,　which　facilitates　collaborative　capture　for　target　molecules,　as　revealed　by　density　functional　theory　(DFT)　calculations.　This　work　uncovers　the　microscopic　mechanism　for　PBDEs　capturing　and　provides　new　insights　into　the　design　of　functionalized　COF　hybrids.　©　2023　Elsevier　B.V.