A　novel　polyhedral　oligomeric　siloxane　(POSS)-based　zwitterionic　monolithic　capillary　column　was　prepared　via　one-pot　polymerization　in　ionic　liquid　porogen,　using　N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)ammonium　betaine　(DMMSA)　and　methacrylic　ethyl　trimethylammonium　chloride　(META)　as　binary　functional　monomers,　and　methacryl　substituted　POSS　as　cross-linker.　The　pore　structure,　permeability　and　homogeneity　were　well　tuned　by　optimizing　the　polymerization　conditions.　The　resultant　monolith　was　characterized　by　scanning　electron　microscopy,　nitrogen　adsorption/desorption　isotherm　and　Fourier　transform　infrared　spectroscopy.　The　incorporation　of　zwitterionic　ligand　(DMMSA),　quaternary　amine　group　(META)　and　rigid　POSS　skeleton　endows　the　hybrid　organic-silica　monolith　with　high　hydrophilicity,　electrostatic　interaction　and　good　mechanical　stability,　as　well　as　a　tunable　electroosmotic　flow　over　wide　pH　range.　A　close　investigation　of　capillary　electrochromatographic　separations　of　different　types　of　polar　compounds　such　as　bases,　nucleosides　and　benzoic　acids　on　such　stationary　phase　exhibited　a　retention　independent　column　efficiency　up　to　118,000　plates/m　(thiourea),　as　well　as　a　mixed-mode　hydrophilic　interaction　chromatography　(HILIC)　retention　mechanism　including　weak　electrostatic　interaction,　hydrophobic　interaction　and　anion　exchange.　©　2021　Elsevier　B.V.