We present a method for analyzing VOCs in mainstream cigarette smoke that allows for high-throughput analysis at a relatively low cost using commercially available materials and equipment. Key features of this method include the appropriate selection of internal standards, inert polyvinylfluoride(PVF)bags for vapor-phase collection,cannula transfer of smoke to an evacuated headspace vial, and subsequent automated solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS).Other advantages include minimal use of solvents, virtually no sample preparation or cleanup required, and no sample carryover. Method validation is discussed along with the analysis of ketones and arenes in 41 cigarette varieties that provide a representative sampling of domestic cigarettes spanning the current range of nicotine deliveries. We also examine the delivery of VOCs as a function of selected cigarette design features and their delivery relative to nicotine delivery