Developing　functional　fiber　coating　for　selective　solid　phase　microextraction　(SPME)　of　trace　pollutants　is　critical　in　environmental　analysis.　Herein,　the　novel　covalent　organic　frameworks　(COFs)　with　three-dimensional　(3D)　frameworks　and　multiple　interactions　were　designed　and　presented　for　the　selective　SPME　of　polychlorinated　biphenyls　(PCBs).　Using　tetra　(p-aminophenyl)　methane　(TAM)　and　1,3,5-triformylphloroglucinol　(Tp)　as　the　monomers,　the　3D　TpTAM-COF　was　synthesized　and　possessed　a　large　specific　surface　area,　high　thermal　stability,　and　spatial　selectivity　toward　PCBs.　Characterizations　such　as　morphology,　XPS,　XRD,　thermal　stability,　and　enhancement　factors　(EFs)　were　studied.　Multiple　interactions　including　π-π　conjugation,　hydrophobic　interaction,　and　selectivity　toward　non-planar　structure　were　adopted,　which　resulted　in　a　superior　adsorption　affinity　toward　PCBs　on　TpTAM-COF.　Under　the　optimal　conditions,　the　spatial　selectivity　toward　PCBs,　organic　analogs　(o-dichlorobenzene,　biphenyl)　and　polycyclic　aromatic　hydrocarbons　(naphthalene,　pyrene,　and　anthracene))　was　achieved.　Efficient　and　selective　adsorption　of　fifteen　PCBs　was　fulfilled　with　the　highest　EF　up　to　10305.　Using　the　HS-SPME-GC-MS　method,　the　recoveries　of　PCBs　in　the　river　water　and　soil　samples　were　determined　to　be　84.8　±　7.8%　∼　117.2　±　8.5%　(n　=　3)　and　84.4　±　8.6%　∼　114.7　±　7.6%　(n　=　3),　respectively.　Compared　with　most　commercial　SPME　fibers　and　other　COFs-based　fibers,　the　resultant　TpTAM-COF-coated　fibers　possessed　higher　selectivity　and　EFs　of　PCBs.　It　proposed　a　promising　approach　for　selective　SPME　of　trace　PCBs　by　multiple　interactions　in　the　steric　structure　of　3D　COFs.　©　2022　Elsevier　B.V.