OBJECTIVE To establish solvent desorption gas chromatograph method for diethylenetriamine determination in workplace air. METHODS Diethylenetriamine in workplace air was collected with alkaline silicone tube, and desorbed with 0. 2 mol/L methanol solution of hydrochloric acid. After centrifugation, the supernatant neutralized with 0. 3 mol/L methanol solution of potassium hydroxide, was separated with 5%-phenyl-methyl polysiloxane(HP-5)(25 m×0. 32 mm×0. 52 mm)and measured with flame ionization detector. RESULTS Detection limit of the method was 0. 49 μg/mL, quantification limit of the method was 1. 64 μg/mL, quantitative determination range of method was 1. 64-233. 80 μg/mL, and the minimum quantitative determination concentration was 0. 22 mg/m~3(based on 7. 5 L sample). The method had a good reproducibility, the relative standard deviation was 1. 4%-3. 3%, the average of desorption efficiency was 90. 8%, and the average of sampling efficiency was 93. 2%. The penetrating capacity of 200 mg alkaline silicone was over than 7. 1 mg, and the samples at room temperature could be preserved for 15 days at least. Ethylenediamine, triethylenetetramine or tetraethylenepentamine coexisted in the air did not interfere during the determination of diethylenetriamine. CONCLUSIONS The method with low determination concentration, high accuracy and precision, is feasible for determination of diethylenetriamine in workplace air.