A　polar　and　neutral　polymethacrylate-based　monolithic　column　was　evaluated　as　a　hydrophilic　interaction　capillary　electrochromatography　(HI-CEC)　stationary　phase　with　small　polar-neutral　or　charged　solutes.　The　polar　sites　on　the　surface　of　the　monolithic　solid　phase　responsible　for　hydrophilic　interactions　were　provided　from　the　hydroxy　and　ester　groups　on　the　surface　of　the　monolithic　stationary　phase.　These　polar　functionalities　also　attract　ions　from　the　mobile　phase　and　impart　the　monolithic　solid　phase　with　a　given　zeta　potential　to　generate　electro-osmotic　flow　(EOF).　The　monolith　was　prepared　by　in　situ　copolymerization　of　a　neutral　monomer　2-hydroxyethyl　methacrylate　(HEMA)　and　a　polar　cross-linker　with　hydroxy　group,　pentaerythritol　triacrylate　(PETA),　in　the　presence　of　a　binary　porogenic　solvent　consisting　cyclohexanol　and　dodecanol.　A　typical　HI-CEC　mechanism　was　observed　on　the　neutral　polar　stationary　phase　for　both　neutral　and　charged　analytes.　The　composition　of　the　polymerization　mixture　was　systematically　altered　and　optimized　by　altering　the　amount　of　HEMA　in　the　polymerization　solution　as　well　as　the　composition　of　the　porogenic　solvent.　The　monoliths　were　tested　in　the　pCEC　mode.　The　resulting　monoliths　had　different　characteristics　of　hydrophilicity,　column　permeability,　and　efficiency.　The　effects　of　pH,　salt　concentration,　and　organic　solvent　content　on　the　EOF　velocity　and　the　separation　of　nucleic　acids　and　nucleosides　on　the　optimized　monolithic　column　were　investigated.　The　optimized　monolithic　column　resulted　in　good　separation　and　with　greater　than　140,000　theoretical　plates/m　for　pCEC.　©　2009　Elsevier　B.V.　All　rights　reserved.