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　bist(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-F　center　dot　center　dot　center　dot　H-C　pseudohydrogen　bonding,　pi-pi　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　(＜8.1%).　Compared　to　the　other　commercial　fiber-based　SPME　methods,　the　IL/POSS　hybrid　coating-based　SPME　is　much　cheaper,　thermally　stable　and　capable　of　eliminating　possible　deleterious　effects　as　well.　(C)　2019　Elsevier　B.V.　All　rights　reserved.