This study investigates the aroma characteristics and key odorants in 'Baimaocha' black teas from three different regions: Rucheng (RCBT), Renhua (RHBT), and Lingyun (LYBT). Comprehensive two-dimensional gas chromatography–olfactometry–quadrupole-time-of-flight mass spectrometry (GC × GC-O-Q-TOFMS) identified 190 volatile compounds, among which 23 were recognized as key odorants contributing to the distinct aroma profiles of the teas. Methyl salicylate, geraniol, trans-β-ionone, and benzeneacetaldehyde were identified as the most definitive aroma compounds for RCBT, RHBT, LYBT, respectively. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) revealed significant differences in volatile compositions among the three regions, with 82 differential volatile compounds identified as potential key aroma compounds. The study also used quantitative descriptive analysis (QDA) to assess sensory attributes, identifying floral, fruity, sweet, roasted, and fresh attributes. PLS analysis further linked specific odorants to these sensory attributes, providing a theoretical basis for controlling and enhancing the aroma quality of 'Baimaocha' black tea.This study investigates the aroma characteristics and key odorants in 'Baimaocha' black teas from three different regions: Rucheng (RCBT), Renhua (RHBT), and Lingyun (LYBT). Comprehensive two-dimensional gas chromatography–olfactometry–quadrupole-time-of-flight mass spectrometry (GC × GC-O-Q-TOFMS) identified 190 volatile compounds, among which 23 were recognized as key odorants contributing to the distinct aroma profiles of the teas. Methyl salicylate, geraniol, trans-β-ionone, and benzeneacetaldehyde were identified as the most definitive aroma compounds for RCBT, RHBT, LYBT, respectively. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) revealed significant differences in volatile compositions among the three regions, with 82 differential volatile compounds identified as potential key aroma compounds. The study also used quantitative descriptive analysis (QDA) to assess sensory attributes, identifying floral, fruity, sweet, roasted, and fresh attributes. PLS analysis further linked specific odorants to these sensory attributes, providing a theoretical basis for controlling and enhancing the aroma quality of 'Baimaocha' black tea.