Benzoapyrene (BaP) in the main stream cigarette smoke was determined by programmed temperature vaporization gas chromatography-mass spectrometry with selective-ion monitoring(PTV-GC/MS-SIM) and large volume injection. The parameters in the determination of BaP in cigarette smoke by PTV-GC/MS-SIM were optimized. Effluents of samples did not required to be concentrated any more after being purified by reverse-phase C18 solid-phase extraction (SPE). Sampling using PTV technology directly increased the utilization ratio of effluents, saved analysis time, and enhanced determination sensitivity of BaP in cigarette smoke by GC/MS-SIM.