Jinjunmei (JJM), Keemun (KM), and Dianhong (DH) are the representative black teas in China, and they have always been favored by consumers. In this study, we aim to obtain the aroma characteristic information of volatile components in black tea samples through headspace solid-phase microextraction (HS-SPME), solvent-assisted flavor evaporation (SAFE), and gas chromatography-mass spectrometry combined with gas chromatography-olfactometry technology. The results showed that 70 compounds including α-methylbenzyl alcohol (isomer of β-phenylethanol) were identified as odorants. Among them, 39 compounds such as linalool and geraniol showed a high degree of aroma contribution. Furthermore, the Feller’s additive model was used to explore the perceptual interactions among the methyl salicylate and the floral compounds (10 groups): five groups of binary compounds showed masking effect after mixing, one group showed additive effect, and four groups showed synergistic effect. The ratio (R) was compared with the aroma index (n) of Steven’s law, which found a high-fitness exponential relationship. The results of this study help to provide additional and new theoretical guidance for improving the aroma quality of black tea.