A　polar　polymethacrylate-based　monolithic　column　was　introduced　and　evaluated　as　a　hydrophilic　interaction　CEC　stationary　phase.　The　monolithic　stationary　phase　was　prepared　by　in　situ　copolymerization　of　a　neutral　monomer　2-hydroxyethyl　methacrylate　and　a　polar　cross-linker　N,N′-methylene　bisacrylamide　in　a　binary　porogenic　solvent　consisting　of　dodecyl　alcohol　and　toluene.　The　hydroxyl　and　amino　groups　at　the　surface　of　the　monolithic　stationary　phase　provided　polar　sites　which　were　responsible　for　hydrophilic　interactions.　The　composition　and　proportion　of　the　polymerization　mixture　was　investigated　in　detail.　The　mechanical　stability　and　reproducibility　of　the　obtained　monolithic　column　preformed　was　satisfied.　The　effects　of　pH　and　organic　solvent　content　on　the　EOF　and　the　separation　of　amines,　nucleosides,　and　narcotics　on　the　optimized　monolithic　column　were　investigated.　A　typical　hydrophilic　interaction　CEC　was　observed　on　the　neutral　polar　stationary　phase.　The　optimized　monolithic　column　can　obtain　high-column　efficiencies　with　62000-126000　theoretical　plates/m　and　the　RSDs　of　column-to-column　(n　=　9),　run-to-run　(n　=　5),　and　day-to-day　(n　=　3)　reproducibility　were　less　than　6.3%.　The　calibration　curves　of　these　five　narcotics　exhibited　good　linearity　with　R　in　the　range　of　0.9959-0.9970　and　linear　ranges　of　1.0-200.0　μg/mL.　The　detection　limits　at　S/N　=　3　were　between　0.2　and　1.2　μg/mL.　The　recoveries　of　the　separation　of　narcotics　on　the　column　were　in　the　range　of　84.0-108.6%.　The　good　mechanical　stability,　reproducibility,　and　quantitation　capacity　was　suitable　for　pressure-assisted　CEC　applications.　©　2013　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.