Objective To establish an analytical method for the determination of methanol and ethanol solvent residues in amidoxime EN chelating agents by headspace gas chromatography.Methods The samples were analyzed in a GC-2030 gas chromatograph system using a Shimadzu HS-20 fully automated headspace injector and quantified by an internal standard method.The samples were separated and detected by the DB-WAX capillary column with a flame ionization detector(FID).The thermostatic furnace temperature was 70 ℃ and the equilibrium time of the sample bottle was 30 min.The sample flow path temperature was 150℃ and the carrier gas was high pure nitrogen.As temperature programming,the initial column temperature of 40 ℃ lasted 9 min and increased to 200 ℃ at 40 ℃/min for 2 min.Results The peak areas of the residual solvents in EN chelator showed good linearity(R2＞0.999)in the mass concentration range investigated,the detection limits of solvent methanol and ethanol were 0.25 μg/mL and 0.30 μg/mL respectively,and the limits of quantification were 1.25 μg/mL and 1.50 μg/mL,respectively.The recovery of residual solvent addition ranged from 97.10％to 102.23％,and the RSD value was less than 5.00％.Conclusion This method is sensitive enough to be used for the determination of solvent residues in amidoxime EN chelating agents.