Magnetic　covalent　organic　frameworks　(Fe3O4@TPPCl4)　were　synthesized　via　a　one-pot　process　in　which　magnetic　nanoparticles　(Fe3O4@MNP)　served　as　a　magnetic　core　and　2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde　(TP)　and　2,2　＇,5,5　＇-tetrachlorobenzidine　(PCl4)　as　two　building　blocks　to　form　a　shell.　The　as-prepared　Fe3O4@TPPCl4　nanoparticles　have　superior　features,　including　large　surface　area　(186.5　m(2)　g(-1)),　high　porosity,　strong　magnetic　responsiveness　(42.6　emu　g(-1)),　high　chlorine　content,　and　outstanding　thermal　stability,　which　make　them　an　ideal　adsorbent　for　highly　selective　enrichment　of　polychlorinated　naphthalenes　(PCNs).　Combining　with　atmospheric　pressure　gas　chromatography　tandem　mass　spectrometry　(APGC-MS/MS),　a　simple　analytical　method　of　Fe3O4@TPPCl4-based　magnetic　solid-phase　extraction　(MSPE)-APGC-MS/MS　was　developed,　which　exhibited　good　linearity　(r　＞=　0.9991)　for　eight　PCNs　in　the　concentration　range　0.1-100　ng　L-1.　Moreover,　low　detection　limits　(0.005-0.325　ng　L-1),　high　enrichment　factors　(46.62-81.97-fold),　and　good　relative　standard　deviations　(RSDs)　of　inter-day　(n　=　3,　1.64　to　7.44%)　and　day-to-day　(n　=　3,　2.62　to　8.23%)　were　achieved.　This　method　was　successfully　applied　to　the　selective　enrichment　of　PCNs　in　fine　particulate　matter　(PM)(2.5)　samples,　and　ultra-trace　PCNs　were　found　in　the　range　1.56-3.75　ng　kg(-1)　with　satisfactory　recoveries　(93.11-105.81%).　The　successful　application　demonstrated　the　great　potential　of　Fe3O4@TPPCl4　nanoparticles　as　an　adsorbent　for　enrichment　of　halogenated　compounds.