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A new method was proposed to detect the BrO3- in tap water by capillary electrophoresis bonded byPHE-calix[4]arene.The buffer was 5 mM phosphate + 0.2 mM CTAB (pH=7.20),and the modified column was 50μm × 50 cm (41.5cm),temperature and separation voltage were 25℃ and -15kV respectively.With thedetermination at 214nm,the calibration curve of BrO3- was y=0.3872x+1.4191 which was linear in the range of10～300 ug/mL with correlation more than 0.997 and the recoveries of 97.60％~99.02％,the detection limit was8ug/mL,the RSD of the peak area and time were 1.15％和0.098％.