Abstract: In order to study the volatile components in cigarette smokers'saliva, a method for analyzing the volatile components in saliva of cigarette smokers by headspace-solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC/MS) was developed. Five human saliva samples collected by Salivette^@ sampling tube were analyzed with this method, and the conditions of headspace sampling, solid phase microextraction and gas chromatography-mass spectrometry were optimized. The results showed that:1)The optimized experimental conditions were:saliva sample 0.5 mL, extracting for 20 minutes at 40℃ by using pink extraction head, headspace sampling after desorbing for 3 minutes, then GC/MS analysis by using elastic quartz capillary column under full scan detection mode. 2)56, 53, 52, 45 and 53 volatile components were detected in saliva samples of smokers smoking "Liqun", "Zhonghua", "Yunyan", "Yuxi" and "Furongwang" respectively. A total of 61 volatile components were detected in 5 saliva samples, including 27 ketones, 11 aldehydes, 2 nitriles, 2 olefinic compounds, 3 esters, 2 alcohols, 5 phenols, 7 heterocyclic compounds and 2 benzene series. The main volatile components were ketones. 3) The results of selected similarity index (SSI) analysis for volatile components from the five samples indicated that the saliva similarities between "Yuxi"-"Zhonghua", "Liqun"-"Furongwang" and "Yunyan"-"Yuxi" were all more than 85%, and the saliva similarities between "Liqun"-"Zhonghua", "Liqun"-"Yunyan" were less than 80%. This method is suitable for the analysis of volatile components in saliva of different cigarette smokers.