Characterizing nicotine delivery from tobacco products is important in the understanding of their addictive potential. Most previous studies report total nicotine and have not differentiated between nicotine in its protonated or free-base form. Rather than simply determining total nicotine, the method described in this paper determines the amount of free-base nicotine associated with trapped mainstream smoke particulate matter generated using a standardized smoking machine protocol. This method quantitatively determines volatile free-base nicotine associated with the particulate phase portion of mainstream cigarette smoke using solid-phase microextraction combined with gas chromatography-mass spectrometry. The headspace above total particulate matter from mainstream cigarette smoke trapped on a Cambridge filter pad (CFP) was analyzed for free-base nicotine in 26 cigarette brands. The selected cigarette brands were chosen to cover a wide range of tar and nicotine deliveries as measured under Federal Trade Commission machine smoking conditions. In the CFP's headspace the free-base nicotine levels ranged from 0.01 to 0.08 mg/cigarette. The measured ranges of free-base nicotine were remarkably similar over the different tar and nicotine delivery categories of full-flavored, light, and ultralight cigarette brands.