The samples of Shanxi aged vinegar before and after aging were analyzed by headspace solid-phase microextraction combined with gas chromatography-mass spectra and gas chromatography-olfactometry. Based on retention indices, mass spectra, and injection of authentic standards, a total of 84 volatile compounds were identified by GC-MS and 42 odor-active compounds were identified by GC-O, including sulfur-containing compounds, nitrogen-containing heterocycles, oxygen-containing heterocycles, aldehydes, ketones, alcohols, acids, esters, phenols and others. For both the vinegars before and after aging, 20 compounds were found in a major amount, such as acetic acid, tetramethyl pyrazine, furfural, furfuryl alcohol, 2,3-butanedione, and so on. Meanwhile 16 compounds were found with high detection frequencies, such as 3-methylthio propanal, 2-ethyl-3,5-dimethyl pyrazine, 2-furanacrolein, vanillin, acetic acid, 3-methyl butanoic acid, and so on. However, according to the total number of compounds, after aging, 14 compounds were newly detected, e.g. 3-methylthio-1-propanol, 2-acetylfurane, benzyl alcohol, and propanoic acid, whereas 19 compounds were disappeared, e.g. dimethyl disulfide, benzyl acetone, butanoic acid, 3-methylpentanoic acid, ethyl butyrate, 2-acetyl pyridine, and 5-hydroxymethyl furfural. According to amounts of the compounds, those of the 11 odoractive compounds (e.g. tetramethyl pyrazine, furfuryl alcohol, phenylethyl alcohol, propanoic acid, and phenethyl acetate) were markedly increased; whereas those of the 29 odor-active compounds (e.g. acetic acid, furfural, hexanoic acid, and benzophenone) were decreased. Overall, the aging processing resulted in decrease of compounds with off-flavors and simultaneously increase of compounds with pleasant flavors. The research results were expected to provide guidance for improving or up-grading the production technology of Shanxi aged vinegar.