BackgroundBaijiu is a very complex system and its flavor substances are endogenous, influenced by raw materials, starter, production process, production region and other factors. The production region directly affects the composition of flavor substances and quality of baijiu. However, identification of baijiu region is challenging because the corresponding relationship between the production region and baijiu quality is not clear, and the identification of regionalmarkers is indeterminate. In this study, the differences in volatile components of sauce‐aroma style baijiu from four representative regions were investigated.ResultsA total of 94 volatile compounds were identified in samples tested. Additionally, it was verified that 35 potential flavor substances had important contributions to the aroma of sauce‐aroma style baijiu. Meanwhile, nine potential regionalmarkers were screened through multivariate analysis. Further, based on distribution of volatile compounds and the results of sensory evaluation combined with multivariate analysis, a molecular matrix and correlation network were established according to the results of addition experiments, which showed that six substances had a significant impact on the flavor of the tested samples.ConclusionSix key flavor substances (ethyl octanoate, ethyl 2‐methylpropanoate, propyl acetate, ethyl heptanoate, 2‐nonanone and butyl hexanoate) were considered as important regionalmarkers to effectively identify the production region of sauce‐aroma style baijiu. © 2023 Society of Chemical Industry.