Six β-Casomorphins were separated and determined by capillary electrophoresis with UV detection.The influence of maximal absorbing wavelength,buffer type,pH value,buffer concentration,separation voltage,injection time on the separation and detection were studied detailedly.Under the optimum condition,six compounds could be separated within 9 min in 30 mmol·L-1 phosphate buffer with pH 11.0.The detection limit range for six β-Casomorphins was 0.34~1.09 μmol·L-1 and range for the theoretical plate number was 1.35×104~7.07×104.