A simple method for the determination of putrescine,spermidine and spermine in hair sample was developed by gas chromatography-mass spectrometry(GC-MS).After alkaline digestion,hair samples were extracted by solid phase extraction(SPE) with diatomaceous earth column,and then derivatized with heptafluorobutyryl chloride(HFB-Cl) in n-hexane.The analytes were determined by a mass spectrometer detector in selected ion monitoring(SIM) mode.A good reproducibility and accuracy were attained.The method was applied to the analysis of the hairs of 14 healthy men and 22 healthy women.Results showed that the most abundant polyamine was spermidine,followed by putrescine and spermine,and the levels of three hair polyamines in men were all found to be higher than in women,respectively.