A method of head-space capillary gas chromatog. (CGC) for the determination of residual solvents in ampicillin sodium and sulbactam sodium mixed powder was established.The residual solvents in ampicillin sodium and sulbactam sodium mixed powder were separated by the Innowax PEG-20M capillary column (30.0 m×0.32 mm×0.25 μm) with the FID detector.The carried gas was nitrogen.The injector temperature and the detector temperature were controlled at 200°C and 250°C, resp.The column temperature was maintained at 40°C.The sample was dissolved in water.The containers of head-space injector were in equilibrium at 80°C for 20 min, the splitting-ratio was 1: 1, water was the solvent.The measured solvents were separated completely.The calibration curve of each solvent showed a good linear relationship with good precision and accuracy.The established method is accurate and reliable, which can be used for the determination of residual solvents in ampicillin sodium and sulbactam sodium mixed powder.