Objective:To develop a capillary electrophoresis system for purity test and enantioseparation of L-pramipexole.Methods: Using β-CD,HP-β-CD,SBE-β-CD and DM-β-CD as chiral selection agents,we investigated the influence of concentration,pH of chiral selection agent and column length and inner diameter on chiral separation.The enantiomers were baseline separated under the following conditions-uncoated fused silica capillary (50 μm × 47 cm) with an effective length of 40 cm,back-ground electrolyte solution:40 mmol/l trisodium citrate buffer solution,0.5% SBE-β-CD,pH 4.0 adjusted by phosphoric acid,5% methanol,25 mmol·L-1 SDS,40 mmol·L-1 sodium tetraborate solution as running buffer,and 16 kV separation voltage.The detection wavelength was set at 254 nm and the column temperature was 30℃.Results: The baseline separation of L-pramipexole was obtained under our condition.The optical isomerism had satisfactory resolution (Rs>2.5) and the content of R-pramipexole was less than 0.5%.Conclusion: The proposed method is simple,reliable and can be used for routine purity test and chiral separation.