Black garlic is a new garlic product produced through fermentation of fresh garlic and is very popular in Asia countries due to its health benefits. Its key aroma-active compounds were characterized by gas chromatography–olfactometry–mass spectrometry (GC-O-MS), gas chromatography–time-of-flight mass spectrometry (GC-TOFMS), and sensory evaluation. In total 52 aroma compounds were identified, and 15 of them with high flavor dilution (FD) factors based on aroma extract dilution analysis (AEDA) were selected and quantitated. Finally, 9 key aroma-active compounds, including acetic acid (sour), allyl methyl trisulfide (cooked garlic), Furaneol (caramel), diallyldisulfide (garlic), diallyltrisulfide (sulfur), (E,Z)-2,6-nonadien-1-ol (cucumber), 3-methylbutanoic acid (sweat), 5-heptyldihydro-2­(3H)-furanone (apricot), and diallyl sulfide (garlic), were determined through aroma recombination and omission experiment. In addition to the sulfur-containing compounds, heterocyclic compounds were the major aroma contributors in black garlic. Sensory evaluation revealed that the flavor profile of black garlic mainly consisted of sulfur, sour, sweet, fresh, sauce, gasoline, and roasted odors.