A capillary electrophoresis method was established for the chiral separation of venlafaxine enantiomers,with trimethyl-hydroxyeth bis(trifluoromethylsulfonyl) imide(HOEtN1,1,1NTf2) and carboxymethyl-β-cyclodextrin(CM-β-CD) as chiral selectors.Influences of CM-β-CD concentration,ionic liquid and buffer concentration,buffer pH value and separation voltage on chiral separation were investigated.The optimal enantioseparation conditions were as follows:background electrolyte(BGE)：20 mmol?L-1 Na2HPO4-H3PO4 buffer(pH 6.0) containing 30 mmol?L-1 HOEtN1,1,1NTf2 and 4.5 mmol?L-1 CM-β-CD,applied voltage:20 kV,detection wavelength:230 nm,sampling time:10 s.Under the optimal enantioseparation conditions,the baseline separation was achieved for venlafaxine enantiomers with resolution of 1.82 in 9 min.The method is of simple operation,fast analysis and good separation effect,which is proved to be suitable for the enantioseparation of venlafaxine.It could also provide a reference for the separation of other chiral drugs.