Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds in the environment, most of which have high toxicity and tumorigenic activity. PAHs are formed during the incomplete combustion of organic matter, so they occur in both mainstream and sidestream cigarette smoke. Benzo[a]pyrene is among the most abundant of PAHs in cigarette smoke, and it is considered to have skin tumorigenic activity many times greater than that of other PAHs. In this paper, a rapid method for isolation and determination of benzo[a]pyrene in the total particulate matter of mainstream cigarette smoke and sidestream cigarette smoke is described. The particulate matter of mainstream cigarette smoke and sidestream cigarette smoke was collected on a Cambridge filter, which was ultrasonically extracted with cyclohexane. A solid phase extraction cartridge with silica stationary phase was used for the isolation of benzo[a]pyrene. The eluate was extracted with acetonitrile and then the extract was evaporated to dryness. The residue was dissolved in acetonitrile before analysis by high-performance liquid chromatography with ultraviolet detection The recovery of benzo[a]pyrene is 94.5%, with a relative standard deviation of 6.95%.