Abstract: With the development of the tobacco industry, rapid, accurate, and high sensitive analysis of tobacco samples has become an inevitable trend and a practical need for the development of the tobacco industry. In this paper, extractive atmospheric pressure photoionization mass spectrometry (EAPPI-MS) was used to directly and rapidly analyze the chemical components in 5 kinds of tobacco products including 1R5F, 3R4F, Derby, Seven Stars, and Wang Guan. This method did not require sample pretreatment and chromatography separation. The whole detection took only one minute for one sample. 46 kinds of chemical components in tobacco including alcohols, ketones, acids, esters, aldehydes, phenols, alkaloids, amino acids, and terpenoids were identified. Compared with the traditional electrospray ionization (ESI), EAPPI has the advantages of nopolar discrimination and higher tolerance to the complex matrix. More than this, more chemical components can be detected by EAPPI-MS than liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS). After comparing the extraction capacity of extraction solvents with different polarities, dichloromethane-methanol (2∶3, V/V) showed a higher extraction effect, which was selected as the optimized extraction solvent. Under optimized parameters, the relative contents of the main alkaloids, organic acids, and phenols in the 5 kinds of tobacco products were analyzed using EAPPI-MS, respectively. Meanwhile, the correlation between the relative contents of tobacco chemicals and tobacco quality was discussed. Overall, different types of tobacco products were unique because of their unique chemical contents. Among these three commercial tobaccos, Derby and Seven Stars were more flavored than Wang Guan. According to the obtained mass spectra of m/z 50-350 using EAPPI-MS, the 5 kinds of tobacco products could be rapidly distinguished using principal component analysis (PCA). EAPPI-MS provides a simple, rapid, and accurate qualitative and quantitative analysis for tobacco chemicals. This method can be used for rapid batch test of chemical components in tobacco leaves and various tobacco products.