A　novel　stationary　phase　phenylaminopropyl　silica　(PhA-silica)　monolith　was　successfully　prepared　for　pressure　assisted　capillary　electrochromatography　(pCEC).　The　monolithic　silica　matrix　from　a　sol-gel　process　was　chemically　modified　by　using　[3(phenylamino)propyl]trimethoxysilane　as　surface　modification　reagent　to　produce　the　phenylaminoporpyl　function.　The　secondary　amino　groups　on　the　surface　of　the　monolithic　stationary　phase　contributed　to　the　generation　of　anodic　electroosmotic　flow　(EOF)　under　acidic　conditions.　The　phenyl　group　together　with　the　spacer　(-(CH2)(3)-)　in　PhA-silica　provides　sufficient　hydrophobic　properties.　To　evaluate　the　column　performance,　effects　of　buffer　pH　and　mobile　phase　composition　on　the　mobile　phase　linear　velocity　and　the　retention　factors　of　alkylbenzenes,　phenols　and　anilines　were　investigated　in　pCEC　mode.　The　monolithic　stationary　phases　exhibit　typical　reversed-phase　(R-P)　electrochromatographic　behavior　toward　neutral　solutes.　Hydrophobic　as　well　as　electrophoretic　migration　process　within　the　monoliths　was　observed　for　the　separation　of　basic　solutes　such　as　anilines　without　peak　tailing.　(c)　2006　Elsevier　B.V.　All　rights　reserved.