A　guanidyl-functionalized　polyhedral　oligomeric　silsesquioxane　(G-POSS)　porous　polymeric　hybrid　coating　was　developed　for　specific　solid-phase　microextraction　(SPME)　of　phthalate　esters　(PAEs),　via　in-situ　click　photopolymerization　on　a　thiolated　stainless　steel　(SS)　fiber.　The　guanidyl-functionalized　L-cysteine　(G-Cys)　monomer　was　fast　copolymerized　with　methacryl　substituted　polyhedral　oligomeric　silsesquioxane　in　the　presence　of　initiator　and　porogen.　The　resultant　G-POSS　hybrid　coating　exhibited　large　specific　surface,　fast　mass　transfer,　and　good　stability　(water-　and　thermal-resistance).　It　showed　mixed-mode　recognition　regime　(hydrogen　bonding,　hydrophobic　interaction　and　＂molecular　sieve　effect＂),　and　therefore　demonstrated　great　benefits　in　SPME　-　gas　chromatography-mass　spectrometry　(GC-MS)　analysis　of　PAEs　with　low　detection　limits　(0.054-2.51　ng　L-1),　wide　linear　range　(1.0-3000.0　ng　L-1),　and　appropriate　repeatability.　The　coating　was　successfully　applied　for　the　enrichment　and　analysis　of　PAEs　in　milk　and　rice　samples.　This　work　indicates　that　the　POSS-based　functionalized　porous　hybrid　polymer　is　a　promising　candidate　for　the　enrichment　of　complicated　samples.