A　simple　thiol-ene　photopolymerization　approach　was　developed　for　the　rapid　preparation　of　ionic　liquid-functionalized　hybrid　monolithic　column　based　on　polyhedral　oligomeric　silsesquioxane　(POSS).　＂One-pot＂　polymerization　was　realized　in　the　UV-transparent　fused-silica　capillary　by　using　octanethiol,　1-allyl-3-methylimidazolium　hexafluorophosphate　as　functional　monomers　and　methacryl-substituted　POSS　as　a　crosslinker.　The　thiol-vinyl-methacrylate　ternary　system　uniquely　exhibits　a　mixed　step-chain　growth　polymerization　regime　that　combining　the　thiol-ene　reaction　and　free-radical　reaction　mechanisms,　which　provides　a　simple　route　to　prepare　novel　POSS-based　functionalized　hybrid　monoliths.　The　pore　property,　permeability,　and　electroosmotic　flow　(EOF)　of　the　hybrid　monoliths　can　be　tailored　by　proper　adjustment　of　the　feeding　composition　and　initiation　condition.　Morphologic　and　spectroscopic　characterizations　of　monolithic　columns　clearly　indicate　that　utilization　of　the　photo-initiated　approach　in　thiol-vinyl　polymerization　can　generate　a　more　homogeneous　porous　structure,　smaller　domain　size　and　higher　column　efficiency　(53,800-60,300　plates/m　for　alkylbenzenes)　than　the　thermally-initiated　one　(32,800-49,300　plates/m).　Significant　improvements　in　mechanical　stability,　anti-swelling　property　and　tailorability　of　hybrid　polymer　were　achieved　in　a　simple　manner,　owing　to　the　photopolymerization　of　rigid　nanoscale　POSS　units　and　imidazolium-based　ionic　liquids　in　ternary　thiol-vinyl　system　for　the　first　time.　The　resulting　hybrid　monolith　possessed　controllable　EOFs　at　pH　values　from　2　to　10,　and　showed　a　multimode　separation　mechanism　in　capillary　electrochromatography,　including　pi-pi　interaction,　ion　exchange,　electrophoretic　migration,　electrostatic　and　hydrophobic　interaction.　Satisfactory　separation　ability　was　achieved　for　the　analysis　of　different　types　of　small　molecules.　(C)　2019　Elsevier　B.V.　All　rights　reserved.