A　new　method　for　rapid　separation　and　sensitive　detection　of　β-blockers　by　pressure-assisted　capillary　electrochromatography　(pCEC)　with　electrospray　ionization　mass　spectrometry　(ESI-MS)　using　silica-based　monolithic　column　was　studied　in　this　paper.　The　proposed　method　has　been　confirmed　to　be　very　powerful　since　the　fast　mass　transfer　property　and　good　permeability　of　silica　monolithic　column　was　used　in　this　pCEC-ESI-MS　system.　In　this　work,　a　silica　monolithic　column　was　prepared　with　sol-gel　method　for　simultaneous　fast　separation　of　β-blockers.　Furthermore,　in　order　to　obtain　the　highly　selective　and　sensitive　result　of　pCEC-ESI-MS,　both　the　CEC　separation　and　MS　detection　parameters　were　optimized　in　detail.　Under　the　optimized　conditions,　namely　80%　acetonitrile　and　20%　20　mmol/L　ammonium　acetate　(pH　6.0)　as　the　mobile　phase,　20　kV　and　8　bar　as　the　separation　voltage　and　the　assisted　pressure,　isopropanol/water　(1:1,　v/v)　containing　7.5　mmol/L　acetic　acid　as　the　sheath　liquid,　and　3　μL/min　as　the　flow　rate　of　sheath　liquid,　seven　β-blockers　were　well　separated　within　11　min　with　detection　limits　in　the　range　of　0.15-0.80　ng/mL　(defined　as　S/N　=　3).　The　recoveries　of　spiked　urine　samples　of　these　β-blockers　were　between　86.3　and　103%　with　the　RSDs　lower　than　8.0%.　The　real　samples　from　some　male　volunteers　were　successfully　analyzed　and　confirmed　with　the　proposed　method.　Comparing　with　GC-MS　or　LC-MS,　the　new　method　has　some　superiority　(such　as　fast　analysis　capacity　and　simple　pretreatment)　in　clinical　practice　and　doping　control.　©　2008　Elsevier　B.V.　All　rights　reserved.