Abstract: In order to investigate the characteristics and differences of flavor substances in Jiangxiangxing Baijiu with different processes (Kunsha, Suisha, Fansha and Chuansha), the contents of total acid, total ester, skeleton flavor substance and odor activity value (OAV) and principal component analysis (PCA) were analyzed. The results showed that the average content of total acid and total ester in Kunsha compared to other process was the highest with significant differences. Meanwhile, the analysis of flavor substances revealed that the flavor substances contents of acids, esters and alcohols in Kunsha were higher than those in the other three groups, and the total content of aldehydes in Fansha was higher than that in Kunsha. In addition, through the PCA of flavor substance content, it was found that different process Jiangxiangxing Baijiu could be distinguished, among which Kunsha had the best clustering effect, the flavor substances that contributed most to it were phenylethyl acetate, ethyl caproate, caproic acid, ethyl palmitate, 2,3-butanediol (meso) and benzaldehyde. OAV demonstrated that ethyl valerate, ethyl caproate, acetaldehyde, acetal and isovalerate contributed significantly to the aroma of Jiangxiangxing Baijiu, and the number of flavor substances with aroma contribution in Kunsha was higher than that in other processes.