A　novel　electroneutral　and　polar　silica-based　hybrid　monolith　was　developed　by　an　in　situ　copolymerization　of　2-hydroxyethylmethacrylate　(HEMA)　and　polyhedral　oligomeric　silsesquioxane　methacryl　substituted　(POSS-MA),　and　successfully　employed　for　hydrophilic　interaction　capillary　electrochromatography　(HI-CEC).　A　good　mechanical　stability　of　the　prepared　monolith　was　gained　with　the　permeability　decreasing　from　6.52×10-14m2　to　4.61×10-14m2　when　mobile　phase　changed　from　ACN　to　water.　A　significant　cathodal　EOF　was　obtained　through　attracting　ions　from　the　mobile　phase　despite　the　fact　that　it　was　devoid　of　ionizable　functional　groups　on　the　surface　of　stationary　phases,　and　a　typical　HI-CEC　mechanism　was　achieved.　The　morphologies　of　the　hybrid　silica-based　monolithic　matrixes　were　observed,　and　the　performance　of　this　silica-based　hybrid　monolith　was　also　investigated.　Satisfactory　column　performances　were　carried　out　for　both　the　neutral　and　charged　analytes　with　HI-CEC.　The　analytes　including　uncharged　amides　and　phenols,　charged　nucleic　acid　bases　and　nucleosides　and　enkephalins,　were　well　separated　with　good　peak　symmetry.　High　separation　efficiencies　of　charged　alkaloids　and　enkephalins　could　get　up　to　145,000plates/m　and　75,000plates/m,　respectively.　©　2012　Elsevier　B.V.