The capillary zone electrophoresis method for chiral separation of valsartan: complete separation of (R,S)-enantiomers of valsartan with a very good resolution (Rs=1.64) was achieved within an untreated fused silica capillary (75μm I.D., effective length was 60 cm). 30 mmol/L sodium acetate and 18 mg/mL β-CD (pH=4.50) was running buffer solution at the detection wavelength of 254 nm. Separation voltage was 20kv and the injection time of sample was 10 s. Results: The separation of both enantiomers of valsartan could be achieved baseline resolution. The calibration curve for valsartan optical isomers exhibited an excellent linear relationship in concentration range of 0.0625mg/mL -1.0mg/mL. The precision was less than 2%. The average recovery was 99.71% and 100.12%. In addition, The detection limit was 1.25μg/mL for valsartan enantiomer was 2.5μg/mL. Conclusion: The method is simple, rapid and accurate. It can be used to quality control the enantiomers of valsartan.