Abstract: Tobacco flavors and fragrances play an important role in improving the aroma quality and smoking taste of cigarettes, and the addition of these ingredients is an important part of the cigarette production process. The rapid characterization of the chemical composition of tobacco flavors and fragrances is necessary for quality control, which is of vital practical significance for improving the stability of cigarette product quality. Compared with other analytical techniques, mass spectrometry has the advantages of high speed, high sensitivity and high specificity. In the past two decades, the direct analysis of complex samples without tedious pretreatment using ambient mass spectrometry has attracted great attention. Here, a low-pressure photoionization mass spectrometry (LPPI-MS) method was used to directly analyze the volatile components of tobacco flavors and fragrances. The volatile species were sucked into the inlet of the mass spectrometer owing to the vacuum pressure difference, and then ionized by the vacuum ultra violet (VUV) light emitted from a krypton discharge lamp. A highly sensitive Orbitrap mass spectrometer with high mass resolution was used as the mass analyzer, and plenty of species were identified with the assistance of tandem mass spectra. The identified species were discussed in combination with the sensory evaluation of target cigarettes. Most of the species identified by traditional gas chromatography-mass spectrometry (GC-MS) could be detected by LPPI-MS, while the analysis time for a single sample is less than 0.5 min, which is much shorter than that of traditional GC-MS. Owing to the high resolution of the Orbitrap mass spectrometer, the isobaric compounds with similar molar masses but distinct molecular formulas in the volatile components of tobacco flavors and fragrances could be precisely characterized, but the isomeric molecules were unable to be differentiated directly by LPPI-MS. Even so, LPPI-MS spectra can provide informative characteristics for a target sample, which is of great value for the differentiation of samples with similar appearances. In order to further validate the applicability of LPPI-MS in the fast screening of tobacco flavors and fragrances, three types of flavors and fragrances used for different brands of cigarettes in the same product series (HS1, HS2 and HS3) were analyzed, and their fingerprint mass spectra were obtained. With the assistance of orthogonal partial least squares discriminant analysis (OPLS-DA), the three kinds of fragrances (fragrance A, fragrance B, fragrance C) and flavors (flavor A, flavor B, flavor C) from different batches were rapidly distinguished and identified, which indicates great application potential in the quality control of large batches of tobacco flavors and fragrances.