A　novel　o-phenanthroline-immobilized　ionic-liquid-modified　hybrid　monolith　for　capillary　electrochromatography　was　synthesized　based　on　chloropropyl-silica,　which　was　prepared　by　the　in　situ　polymerization　of　tetramethoxysilane　and　3-chloropropyltrimethoxysilane　via　a　sol-gel　process.　The　morphology　of　the　hybrid　monolith　was　characterized　by　scanning　electron　microscopy,　and　relatively　stable　anodic　electroosmotic　flow　was　observed　under　a　broad　pH　ranged　from　pH　3.0　to　9.0.　The　separation　mechanism　was　investigated　by　separating　four　neutral　molecules　(toluene,　dimethylformamide,　formamide,　and　thiourea).　The　obtained　hybrid　monolith　possessed　an　obviously　reversed-phase　retention　mechanism,　but　when　the　acetonitrile　content　in　the　mobile　phase　was　＞90%　v/v,　a　weak　hydrophilic　mechanism　was　observed　on　the　resultant　o-phenanthroline-modified　chloropropyl-silica　hybrid　monolith.　The　reproducibility　of　the　column　was　also　investigated　by　measuring　relative　standard　deviations　of　the　migration　time　for　four　neutral　molecules.　Relative　standard　deviations　of　run　to　run　(n　=　3),　day　to　day　(n　=　3),　and　column　to　column　(n　=　3)　were　in　the　range　of　0.4-0.7,　0.9-2.1,　and　1.4-3.3%,　respectively.　Basic　separations　of　various　polar　analytes　including　phenols　and　aromatic　amines　were　successfully　achieved.　©　2014　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.