Capillary electrophoresis (CE) and chiral stationary phase (CSP) HPLC methods were investigated for the determination of enantiomeric purity of alpha1-adrenoreceptor antagonists related to WB 4101. In the CE study, the enantioseparation of the analytes was performed by studying the effect of different types of cyclodextrin in the buffer, namely heptakis (2,6-di-O-methyl)-beta-cyclodextrin (DMCD), hydroxypropyl-beta-cyclodextrin (HPCD) and beta-cyclodextrin (beta-CD). HPCD was found to be the most effective chiral selector in the enantioseparation of all the compounds, with high resolution values. A HPLC method, using immobilised serum protein columns, human serum albumin (HSA) and alpha1-acid glycoprotein (AGP), was also investigated. Two benzodioxane racemates were well resolved on a mixed tpe (50% HSA and 50% AGP) column, with enantioselective binding on AGP column.