A novel gas chromatography-mass spectrometric(GC-MS) method coupled with purge and trap was developed for the simultaneous determination of nine neutral volatile polyfluorinated iodine alkanes(PFIs) in water samples.Several P&T parameters such as type of traps,purge time,purge temperature,desorbing time and ionic strength were optimized.Under the optimal conditons,the calibration curves for the nine PFIs showed good linear relationships(r2≥0.996) in the concentration range of 0.1-100 μg·L-1.The limits of detection(LOD) ranged from 5.6 ng·L-1 to 15 ng·L-1,and the limits of quantitation were from 17 ng·L-1 to 36 ng·L-1.The spiked recoveries for the analytes in water samples were in the range of 75.7%-118% with relative standard deviations(RSDs,n=7) of 2.2%-83%.The method was applied in the detection of volatile PFIs in water samples from the vicinity of a fluorochemical manufacturing plant,and nine PFIs were detected,with concentrations of 21.3-469 ng·L-1.