Volatile constituents in jambolan [Syzgium cumini (L.) Skeels] wine were isolated by headspace–solid phase microextraction (HS–SPME) and analyzed by gas chromatography-flame ionization detector (GC–FID), gas chromatography-mass spectrometry (GC–MS), and gas chromatography–olfactometry (GC–O). The composition of the jambolan wine included 52 esters, 20 terpenes, 13 alcohols, 12 acids, 11 aldehydes, 4 ketones, 4 oxides, and 5 miscellaneous compounds. Aroma extract dilution analysis and odor activity units were used for the determination of odor-active compounds. A total of 19 odor-active compounds were found as odor-active volatiles, from which (E)-β-ionone, phenylacetaldehyde, ethyl acetate, ethyl hexanoate, and ethyl benzoate were the most important. The similar results of the GC–O and OAV approaches suggests that HS–SPME–GC–O could be used as a fast and simple tool to quality control of the jambolan wine aroma.