A　direct　immersion　solid-phase　microextraction　(DI-SPME)　approach　for　gas　chromatography-mass　spectrometry　(GC–MS)　based　on　hybrid　fiber　coating　of　ionic　liquid　and　polyhedral　oligomeric　silsesquioxane　(POSS)　is　presented.　To　fabricate　the　task-specific　coating　for　the　enrichment　of　polycyclic　aromatic　hydrocarbons　(PAHs),　1-butyl-3-vinylimidazolium　bis[(trifluoromethyl)sulfonyl]imide　(IL)　and　POSS　were　rapidly　photoinitiated　copolymerized　within　5　min　on　a　stainless　steel　fiber.　The　high　efficient　extraction　of　target　analytes　can　be　attributed　to　a　combined　result　of　multiple　interactions　including　the　strong　C–FH–C　pseudohydrogen　bonding,　π-π　stacking,　hydrophobic　force,　and　molecular　sieve　effect.　A　wide　linear　range　(0.04–400　ng　L−1)　with　low　detection　limits　in　the　range　of　0.004　and　0.5　ng　L−1　were　obtained　for　PAHs　by　GC–MS.　The　applicability　of　this　coupling　method　was　successfully　demonstrated　by　the　analysis　of　trace　PAHs　in　real　river　water　and　soil　samples,　with　satisfied　recoveries　(84.2–108.6%)　and　relative　standard　deviations　(　©　2019　Elsevier　B.V.