The aroma profile of sun-dried black tea (SBT) was identified by headspace solid–phase microextraction (HS–SPME) coupled with gas chromatography–mass spectrometry (GC–MS) and gas chromatography–olfactometry (GC–O). A total of 37 scents were captured by using the GC–O technique, and 35 scents with odor intensities ranging from 1.09 ± 1.93 to 9.91 ± 0.29 were identified. Twenty-one compounds were further identified as key odor-active compounds with odor activity values (OAVs) greater than or equal to one. These key odor-active compounds were restructured with their detected concentrations, and the aroma profile of the selected SBT sample was successfully imitated to a certain extent. An omission test was performed by designing 25 models and confirmed that (E)-β-damascenone, β-ionone, dihydro-β-ionone, linalool, and geraniol were the key odor-active compounds for the aroma profile of SBT. Meanwhile, phenylethyl alcohol, (E)-2-decenal, hexanal, and methyl salicylate were also important to the aroma profile of SBT. This study can provide theoretical support for the improvement of the aroma quality of sun-dried black tea.