Electro-enhanced　solid-phase　microextraction　(EE-SPME)　is　a　bright　separation　and　enrichment　technique　that　integrates　solid-phase　microextraction　with　the　electric　field.　It　retains　the　excellent　extraction　performance　of　SPME　technology　while　having　the　advantages　of　efficient　driving　of　electric　field　and　special　interaction　between　the　electric　field　and　electrons　in　the　molecules　of　material　structure.　Replacing　conventional　SPME　fibers　with　highly　efficient　and　highly　conductive　original　EE-SPME　fibers　is　critical　for　the　practical　applications　of　these　technologies.　Here,　a　novel　fiber　preparation　strategy　was　proposed　to　obtain　a　highly　conductive　porphyrin-based　covalent　organic　framework　(POR-COF)　by　one-step　electropolymerization.　Benefiting　from　the　excellent　semiconducting　properties　of　porphyrin　groups,　the　POR-COF　can　be　spontaneously　polymerized　on　the　fiber　surface　under　an　appropriate　voltage　within　a　few　hours.　Its　performance　was　evaluated　by　the　EE-SPME　of　phthalate　esters　(PAEs)　from　food　and　environmental　samples,　followed　by　gas　chromatography-tandem　triple　quadrupole　mass　spectrometry　(GC-MS/MS)　technology.　The　results　showed　that　the　POR-COF　fiber　has　been　successfully　used　for　the　detection　of　trace　PAEs　in　beverages,　industrial　wastewater,　lake　water,　and　oyster　samples　with　high　adsorption　selectivity　and　satisfactory　sensitivity.　The　remarkable　extraction　properties　are　mainly　attributed　to　the　synergistic　effect　from　material　characteristics　and　electrical　parameters’　control　in　the　extraction　process.　The　presented　strategy　for　the　controlled　design　and　synthesis　of　highly　conductive　porphyrin-based　covalent　organic　framework　fibers　offers　prospects　in　developing　EE-SPME　technologies.　©　2023　American　Chemical　Society.