An　ionic　liquid　hybrid　monolithic　capillary　column　was　prepared　within　7　min　via　photoinitiated　free-radical　polymerization　of　an　ionic　liquid　monomer　(1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide);　VBIMNTF2)　and　a　methacryl　substituted　polyhedral　oligomeric　silsesquioxane　(POSS-MA)　acting　as　a　cross-linker.　The　effects　of　composition　of　prepolymerization　solution　and　initiation　time　on　the　porous　structure　and　electroosmotic　flow　(EOF)　of　monolithic　column　were　investigated.　The　hybrid　monolith　was　characterized　by　scanning　electron　microscopy　and　FTIR.　Owing　to　the　introduction　of　a　rigid　nanosized　POSS　silica　core　and　ionic　liquids　with　multiple　interaction　sites,　the　monolithic　column　has　a　well-defined　3D　skeleton　morphology,　good　mechanical　stability,　and　a　stable　anodic　electroosmotic　flow.　The　hybrid　monolithic　stationary　phase　was　applied　to　the　capillary　electrochromatographic　separation　of　various　alkylbenzenes,　phenols,　anilines　and　polycyclic　aromatic　hydrocarbons　(PAHs).　The　column　efficiency　is　highest　(98,000　plates/m)　in　case　of　alkylbenzenes.　Mixed-mode　retention　mechanisms　including　hydrophobic　interactions,　pi-pi　stacking,　electrostatic　interaction　and　electrophoretic　mobility　can　be　observed.　This　indicates　the　potential　of　this　material　in　terms　of　efficient　separation　of　analytes　of　different　structural　type.