Abstract: For simply and sensitively determining the vinyl chloride in mainstream cigarette smoke, a gas chromatography-mass spectrometry (GC/MS) method was developed, where the particulate matter in mainstream smoke was trapped with Cambridge filter pads and gas phase cold trapped with two absorption bottle in series (methanol solution as absorbing liquid). The vinyl chloride contents in gas phase of mainstream smoke of 23 domestic and imported cigarettes with different tar deliveries were determined by the developed method. The results showed that: 1) The detection limit of vinyl chloride was 2.0 ng/cig. and the recovery ranged from 95.0% to 97.4%. The intra-day and inter-day precisions were less than 6% and 8%, respectively. 2) The vinyl chloride contents in mainstream smoke of the 23 cigarettes ranged from 20.0 to 74.8 ng/cig. This method is simple, rapid, accurate and suitable for the determination of vinyl chloride in cigarette smoke.