Longjing tea is the most famous premium green tea, and is regarded as the national tea in China, with its attractive aroma contributing as a prime factor for its general acceptability; however, its key aroma compounds are essentially unknown. In the present study, volatile compounds from Longjing tea were extracted and examined using stir bar sorptive extraction (SBSE) combined with gas chromatography-mass spectrometry (GC-MS). Data obtained from the present study revealed that 151 volatile compounds from 16 different chemical classes were identified by GC-MS analysis. Enols (8096 µg/kg), alkanes (6744 µg/kg), aldehydes (6442 µg/kg), and esters (6161 µg/kg) were the four major chemical classes and accounted for 54% of the total content of volatile compounds. Geraniol (6736 µg/kg) was the most abundant volatile compound in Longjing tea, followed by hexanal (1876 µg/kg) and β-ionone (1837 µg/kg). Moreover, 14 volatile compounds were distinguished as the key aroma compounds of Longjing tea based on gas chromatography-olfactometry (GC-O) analysis, odor activity value (OAV) calculations, and a preliminary aroma recombination experiment, including 2-methyl butyraldehyde, dimethyl sulfoxide, heptanal, benzaldehyde, 1-octen-3-ol, (E, E)-2,4-heptadienal, benzeneacetaldehyde, linalool oxide I, (E, E)-3,5-octadien-2-one, linalool, nonanal, methyl salicylate, geraniol, and β-ionone. This is the first comprehensive report describing the aroma characterizations and the key aroma compounds in Longjing tea using SBSE/GC-MS. The findings from this study contribute to the scientific elucidation of the chemical basis for the aromatic qualities of Longjing tea.