Sitafloxacin epimers were separated by capillary zone electrophoresis using gamma-cyclodextrin (gamma-CD) and D-phenylalanine (D-Phe) as chiral selector. The effects of the concentrations of gamma-CD, D-Phe, Cu2+ and pH of buffer were investigated. An uncoated fused-silica capillary of 50 microm i.d. and 60 cm (effective length 52.5 cm) was used. The capillary temperature was maintained at 25 degrees C. Samples were injected under a pressure of 7 kPa for 5 s and separated at 15 kV. A baseline separation of sitafloxacin epimers was achieved with a background electrolyte of 10 mmol/L KH2PO4-K2HPO4(pH 4.5), 10 mmol/L CuSO4, 20 mmol/L gamma-CD and 10 mmol/L D-Phe. The linear range for sitafloxacin was 32 -400 mg/L (0.996). The relative standard deviations (RSDs) of migration time and peak area were less than 1.9% and 3.8% respectively. This method can be applied in qualitative and quantitative analysis for sitafloxacin epimers.