The aromatic characteristics of Xiaoqu Baijiu differ noticeably and were investigated using the sensomics approach. Aroma extract dilution analysis revealed more aroma-active compounds in aged Xiaoqu Baijiu than fresh Xiaoqu Baijiu, with 55 compounds identified with flavor dilution (FD) factors of ≥8. Using sensomics, 51 odorants were identified as important aroma compounds in aged Xiaoqu Baijiu. Omission models suggested that 3-hydroxy-4,5-dimethyl-2(5H)-furanone (sotolon), vanillin, and 3-(methylthio)propionaldehyde (methional) played critical roles in the overall aroma characteristics of aged Xiaoqu Baijiu. Furthermore, 1,1-dimethoxyethane, 3-methylbutanal, dimethyl trisulfide, ethyl acetate, and ethyl isovalerate also exhibited significant roles in the aroma characteristics of aged Xiaoqu Baijiu. This work may provide a better understanding on Chinese Xiaoqu Baijiu and the changes of aroma compounds during the aging process of liquor.