A　pressurized　capillary　electrochromatography　(pCEC)　with　monolithic　column　has　been　developed　for　the　rapid　separation　and　determination　of　five　structurally　related　anthraquinones　in　Rhubarb.　The　possibility　of　rapid　separation　resulted　from　the　unique　pore　structure　with　high　permeability　and　favorable　mass　transfer　characteristics　of　the　monolithic　stationary　phase.　The　effect　factors　such　as　organic　modifier,　acidity　and　concentration　of　running　buffer,　separation　voltage　were　investigated　to　acquire　the　optimum　condition.　In　the　220　nm　wavelengths,　the　five　anthraquinones　could　be　baseline-separated　rapidly　within　5　min　with　the　separation　voltage　of　-20　kV　in　10　mmol/L　phosphate　buffer　(pH　6.2)　containing　65%　acetonitrile.　The　calibration　graphs　of　them,　aloe-emodin,　emodin　chrysophanol　and　physcion　were　linear　by　plotting　the　peak　area　against　the　analytes　concentration　over　the　range　of　0.2-65,　0.1-30,　0.1-55,　0.5-30　and　0.5-55　mu　g/mL,　respectively.　The　detection　limits　of　five　anthraquinones　were　ranged　from　0.06　to　0.2　mu　g/mL　and　the　recoveries　of　Rhubarb　samples　were　about　81.3-86.4%　(R.S.D.　＜=　5.2%).　This　proposed　method　was　successfully　applied　to　determination　of　the　five　analytes　in　Rhubarb　with　satisfactory　results.　(c)　2006　Elsevier　B.V.　All　rights　reserved.