Efficient　fabrication　of　excellent　fiber　coatings　for　high-performance　solid-phase　microextraction　(SPME)　is　interesting.　Here,　a　high-efficiency　synthesis　strategy　on　graphene　oxide/polyhedral　oligomeric　silsesquioxane　(GO/POSS)　composite-coated　fiber　was　exploited　via　an　ultra-fast　UV　polymerization　in　one　step,　and　applied　to　excellent　SPME　of　polycyclic　musks　(PCMs).　Using　methacryloxy　siloxane-grafted　GO　and　POSS-methacryl　substituted　(POSS-MA)　as　functional　monomers,　a　facile　and　direct　UV　polymerization　of　multiple　reactions　including　alkenyl　radical　reaction　and　thiol-ene　click　chemistry　was　fulfilled　on　thiol-pretreated　fiber　in　only　5　min　without　tedious　process.　Characteristics　such　as　morphology,　FT-IR,　XPS,　BET　and　TG　of　fiber　coating　were　studied　in　detail,　as　well　as　the　SPME　performance.　Attributing　to　the　rigid　stereo　conformation　of　POSS　and　large　conjugate　plane　of　GO-based　nanosheet,　the　significant　surface　area,　high　hydrophobicity　and　intrinsic　π-π　interactions　were　adopted　in　fiber　coating.　In　comparison　of　commercial　SPME　fibers,　POSS-based　or　GO-based　SPME　fibers,　a　superior　extraction　performance　towards　PCMs　was　achieved　with　GO/POSS-coated　fiber.　High-efficiency　extraction　of　PCMs　was　gained　with　prominent　enrichment　factors　and　the　sensitive　detection　limits　of　PCMs　were　of　0.04–0.12　ng/L.　In　particular,　the　extraction　efficiency　was　robust　and　still　maintained　a　high　level　above　93%　for　PCMs　even　after　150　cycle＇s　applications.　Good　recoveries　of　PCMs　reached　86.6%–102.1%　and　86.7%–101.3%　in　river　water　and　cosmetic　samples,　respectively.　It　lights　an　attractive　approach　to　efficiently　fabricating　robust　GO/POSS-coated　fiber　for　high-performance　SPME　of　PCMs.　©　2022　Elsevier　B.V.