Abstract: In odrer to accurately analyze the residue of volatile ketone, alcohol, esters, nitriles in wastewater, the method was established to determine 16 kinds of volatile Ketones, Alcohols, Esters, Nitriles in wastewater by headspace-gas chromatography-mass spectrometry. The analysis was carried out with a capillary column DB-624（30 m×0.32 mm×1.8 μm）under electron ionization conditions at a flow rate of 1.5 mL/min，the qualitation was performed by the mode of scanning and the quantitation was performed by the external standard method using selected ion. The results showed that all calibration curves of 16 kinds of compounds had good linearity for acrylonitrile (r>0.999 5)．The detection limits were in the range of 0.04—0.95 mg/L when using 10.0 mL wastewater samples. At three different concentration levels, the average recoveries of 16 kinds of compounds in spiked practical wastewater samples were in the range of 89.2%—118% with relative standard deviation of 0.32%—7.61%. The method can rapidly and accurately monitor sixteen kinds of volatile Ketones, Alcohols, Esters, Nitriles in wastewater.