The samples of Shanxi aged vinegar before and after aging were treated by simultaneous distillation and solvent extraction （SDE）. The extracts from the two vinegars were analyzed by gas chromatography-mass spectra （GC-MS） and gas chromatography-olfactometry（GC-O）. Based on retention indices， mass spectra， and injection of authentic standards， a total of 184 volatile compounds were identified， including sulfur-containing compounds， nitrogen-containing heterocycles， oxygen-containing heterocycles， aldehydes， ketones， alcohols， acids， esters， phenols， ethers， and others. The major volatile compounds found in both the vinegars before and after aging included acetic acid， acetoin， furfural， 2，3-butanedione， etc. However， compared to the vinegar before aging， the amounts of pyrazine compounds， especially tetramethylpyrazine， were markedly increased in the aged vinegar. By GC-O analysis， according to retention indices， sniffed odor characteristics， identifications in the GC-MS， and comparison of the analytical parameters with those of the authentic standards， a total of 23 odor-active compounds were identified， where 10 compounds were found with high FD values in the vinegar before aging， including acetic acid， acetoin， 2，3-butanedione， ethyl lactate， guaiacol， etc； and 20 compounds were found with high FD values in the vinegar after aging， including 3-methyl propyl alcohol， furfural， phenylacetyldehyde， guaiacol， etc. Comparatively， after aging mainly the odorants of esters were decreased while those of the nitrogen-containing heterocyclic compounds （especially the pyrazine compounds） and the sulfur-containing compounds were increased in the vinegars. The research results are expected to provide guidance for upgrading production technology of the Shanxi aged vinegar.