Tobacco products generally contain tobacco-derived nicotine (TDN; having ∼99+% (S)-(−)-nicotine). Recent United States regulation has led some producers to transition to synthetic (“tobacco-free”) nicotine. For example, Puff Bar is now marketed with tobacco-free nicotine (TFN; presumed to be racemic). To evaluate the claim that these new products contain TFN, we evaluated the presence of the two nicotine optical isomers by 1H NMR spectroscopy, polarimetry, and gas chromatography–mass spectrometry. Older Puff Bars were found to contain (S)-(−)-nicotine, and newer “TFN” Puff Bars were found to contain both (R)-(+) and (S)-(−) isomers—indicating TFN, albeit with slightly more of the (S)-(−)-nicotine form.