Sichuan black tea (SCBT) is well known for its pleasant sweet and citrus-like aroma. However, the origin of this distinctive aroma remains unknown. Herein, the aroma characteristics of SCBT during processing were comprehensively investigated by sensory evaluation, gas chromatography–mass spectrometry, and odor activity value (OAV). A total of 764 volatile compounds were identified and grouped into 16 categories. Notably, terpenoids, heterocyclic compounds, and esters comprised 19.35%, 16.34%, and 16.08% of total volatile compounds produced during processing, respectively. Moreover, the fermentation and second drying stages exhibited the most striking variations, with 99 and 123 volatile compounds being significantly altered. In addition, the OAV analysis led to the identification of 17 volatile compounds as key differential volatile compounds (DVCs): these included citronellol, linalool, p-cymene, (E)-linalool oxide (furanoid), etc. Among them, (3Z)-3,7-dimethylocta-1,3,6-triene and D-limonene that exhibited a grassy aroma decreased during processing, while linalool and p-cymene that had a sweet and citrus aroma increased. Thus, based on a correlation between characteristic aroma data and descriptive sensory analysis data, linalool and p-cymene were identified as the primary volatiles responsible for the sweet and citrus-like aroma. In conclusion, this study improves our understanding of the components and formation mechanism of the sweet and citrus-like aroma of SCBT.