Stir bar sorptive extraction (SBSE) combined with gas chromatography-mass spectrometry (GC-MS) was used to detect the volatile composition of 20 Anjibaicha samples, and gas chromatography-olfactometry-mass spectrometry (GC-O-MS) combined with relative odor activity value (ROAV) was utilized to identify its key aroma-active compounds. Results showed that 109 volatile compounds were detected in the tea samples. Among them, geraniol, diisobutyl phthalate, phytol, methyl salicylate, cis-jasmone, linolenic acid, and linalool were the most abundant components. It was found that the contents of volatile components in different grades of Anjibaicha varied greatly. Moreover, a total of 34 common characteristic peaks were selected to establish a fingerprint of the volatile components of Anjibaicha. Sixteen compounds were identified as key aroma-active compounds of Anjibaicha, including trans-β-ionone, geraniol, linalool, hexanal, heptanal, (E)-2-heptenal, α-ionone, and (Z)-3-hexenyl hexanoate.