A capillary electrophoresis coupled with electrochemiluminescence detection(CE-ECL)was successfully developed for the chiral separation and determination of a kind of antidepressants racemic drug(venlafaxine) enantiomers by employing sulfated β-cyclodextrin(S-β-CD)as the chiral selector.The determination conditions,including inlet and outlet buffers,injection time and voltage,separation voltage and detection potential were optimized.Unlike the traditional chiral separation method,the buffers used in the capillary inlet and outlet differed from each other.Under the optimum conditions,baseline enantioresolution and highly sensitive detection for the enantiomers of venlafaxine were achieved.The results showed that there was a linear relationship between Luminous intensity(I) and two venlafaxine enantiomers(S,R) concentrations(ρ) in the range of 0.1 μg/L to 1 000 μg/L.And the linear regression equations were IS=321.5ρ+30.1(r=0.999 6) and IR=319.3ρ +28.4(r=0.999 4),respectively.The detection limits(S/N=3) were obtained to be 0.01 μg/L and 0.05 μg/L，respectively,which were lower than the reported value about 3 orders of magnitude.The recoveries were in the range of 94%-100% with relative standard deviations no more than 3.2%.Therefore,the CE-ECL method has the application potential in chiral separation,and could be used to detect drug enantiomers in clinical pharmacology.