An　improved　technique,　pressurized　capillary　electrochromatography　(pCEC)　coupling　with　end-column　amperometric　detection　(AD),　was　developed　and　used　for　the　separation　and　determination　of　estrogens.　The　effects　of　pH　value,　composition　of　mobile　phase,　concentration　of　the　surfactant　sodium　dodecyl　sulfate　(SDS)　and　applied　voltage　on　separation　were　investigated.　The　electrochemical　oxidation　of　diethylstilbestrol　(DES),　dienestrol　(DE),　and　hexestrol　(HEX)　could　be　reliably　monitored　with　a　carbon　electrode　at　0.9　V　(vs.　Ag/AgCI).　The　pCEC　analyses　were　performed　on　a　capillary　separation　column　packed　with　3　μm　C18　particles　with　an　acetonitrile/water　(31%:　69%)　mobile　phase　containing　Tris　buffer　(5　mmol/L,　pH　4.5)　and　4　mmol/L　SDS.　High　voltage　up　to　12　kV　reduced　the　retention　time　dramatically　and　still　provided　a　baseline　resolution.　In　addition,　supplementary　pressure　prevented　bubble　formation　and　provided　reliability　and　reproducibility　of　the　pCEC　performance.　The　detection　limits　for　the　three　estrogens　ranged　from　1.2　to　2.2　×　10-7　mol/L,　about　10∼20-fold　lower　than　those　obtained　with　pCEC-UV　detection.　To　evaluate　the　feasibility　and　reliability　of　this　system,　the　proposed　pCEC-AD　method　was　further　demonstrated　with　fish　muscle　samples　spiked　with　estrogens.　©　2005　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.