Abstract: To investigate the differences in flavor composition of Jiang-flavor Baijiu from different production areas in the Chishui River basin, the gas chromatography-flame ionization detector was used to analyze differences in the flavor characteristics and sensory profiles of samples from the downstream Linhe (XY), Maotai valley (MT), and Hedong low-medium mountain (HD) production areas. The results revealed that sauce aroma was prominent and the Baijiu body was plump in MT production area, whereas in the XY production area, there was a notable grass fragrance and the Baijiu body was clean, and in the HD production area the Baijiu was sweet. On the basis of analysis of flavor substances in Baijiu samples collected from the different production areas, the highest total content of volatile substances was observed in the MT Baijiu samples, while the lowest was observed in the HD Baijiu samples. Moreover, notable differences in the contents of acids, aldehydes and ketones, aromatics, and pyrazines were detected in samples from the different production areas. Analysis of aroma activity values revealed that phenethyl acetate, ethyl hexadecanoate, 2-butanol, 3-methyl-1-butanol, and 1-octanol were the main volatiles contributing to differences in the flavor of Baijiu from the three production areas. Orthogonal partial least squares discriminant analysis could effectively establish the production area classification model, and combined with the variable importance for the projection value. Eight potential differential compounds were identified, namely ethyl lactate, ethyl acetate, acetaldehyde, 1-propanol, 3-methyl-1-butanol, acetic acid, propionic acid and acetal. Furthermore, the results of correlation analysis revealed that acetaldehyde and acetal, 1-propanol and ethyl phenylacetate, ethyl octanoate, and 1-butanol were significantly correlated with grassy, Qu, floral and fruity, and spicy flavors, respectively. The results of this study will aid consumers in understanding and selecting among the Jiang-flavor Baijiu systems in different production areas.