This study characterized key odorants in 'Baimaocha' black teas from three regions: Rucheng (RCBT), Renhua (RHBT), and Lingyun (LYBT). Using comprehensive two-dimensional gas chromatography-olfactometry-quadrupole-time-of-flight mass spectrometry (GC × GC-O-Q-TOMS), 190 volatile compounds were identified, with 23 recognized as key odorants contributing to distinct aroma characteristics. The odor activity values (OAV) combined with GC-O analysis identified methyl salicylate (RCBT), geraniol (RHBT), and trans-β-ionone and benzeneacetaldehyde (LYBT) as the most definitive aroma compounds. PLS analysis revealed three odorants as significant contributors to floral characteristics, four to fruity, four to fresh, and three to roasted attributes. These findings provide insights into the sensory evaluation and chemical composition of 'Baimaocha' black tea, offering a theoretical basis for controlling and enhancing tea aroma quality. The study also identified key aroma-active compounds through GC-O techniques, highlighting the importance of volatile compounds in defining the unique aroma profiles of each region's 'Baimaocha' black tea. The results underscore the role of specific volatile compounds in shaping the distinct sensory attributes of 'Baimaocha' black teas from different regions.This study characterized key odorants in 'Baimaocha' black teas from three regions: Rucheng (RCBT), Renhua (RHBT), and Lingyun (LYBT). Using comprehensive two-dimensional gas chromatography-olfactometry-quadrupole-time-of-flight mass spectrometry (GC × GC-O-Q-TOMS), 190 volatile compounds were identified, with 23 recognized as key odorants contributing to distinct aroma characteristics. The odor activity values (OAV) combined with GC-O analysis identified methyl salicylate (RCBT), geraniol (RHBT), and trans-β-ionone and benzeneacetaldehyde (LYBT) as the most definitive aroma compounds. PLS analysis revealed three odorants as significant contributors to floral characteristics, four to fruity, four to fresh, and three to roasted attributes. These findings provide insights into the sensory evaluation and chemical composition of 'Baimaocha' black tea, offering a theoretical basis for controlling and enhancing tea aroma quality. The study also identified key aroma-active compounds through GC-O techniques, highlighting the importance of volatile compounds in defining the unique aroma profiles of each region's 'Baimaocha' black tea. The results underscore the role of specific volatile compounds in shaping the distinct sensory attributes of 'Baimaocha' black teas from different regions.