Systematic Comparison of Aroma Profiles and Tea Polysaccharide In Vitro Antioxidant Activities Among Six Anxi Oolong Tea Cultivars

Oolong tea is prized for its floral aroma and bioactive tea polysaccharides (TPS), yet the independent contribution of cultivar genetic background to aroma chemistry and TPS functionality remains unclear due to confounding effects from environment and processing. Here, we systematically compared volatile organic compound (VOC) profiles and in vitro antioxidant activities of TPS from six Anxi oolong tea cultivars all grown in the same tea garden and processed under identical Qingxiang oolong tea protocols. Using headspace solid-phase microextraction-gas chromatography-mass spectrometry, 39 VOCs were identified across cultivars. Huangjingui exhibited the highest total VOC content (69.01 μg·g−1) and the greatest number of compounds with relative odor activity values (rOAV) over 1. Principal component analysis and hierarchical clustering revealed clear metabolic separation among cultivars, with Daye Wulong displaying the most distinct metabolome. PLS-DA combined with rOAV screening identified 12 key differential volatiles that form the chemical basis of floral aroma. Preliminary in silico molecular docking predicted the strongest binding affinity between nerolidol and OR1A1 (−7.54 kcal/mol). Cultivar-specific high rOAV volatiles were characterized, including (E)-2-octenal and 1-phenyl-2-nitroethane in Tieguanyin, 2-phenylethyl-2-methylbutyrate and cis-3-hexenyl isovalerate in Maoxie, α-ocimene and cis-3-hexenyl benzoate in Daye Wulong, and (E,E,Z)-1,3,5,8-undecatetraene in Meizhan, suggesting their potential as chemical markers for cultivar authentication. Crude TPS yields ranged from 2.76% to 3.99%; Tieguanyin had the highest yield and Meizhan the lowest. TPS from Daye Wulong exhibited the strongest DPPH and ABTS+· scavenging capacities, with IC50 values of 0.58 and 1.95 mg·mL−1, respectively, indicating the highest in vitro antioxidant activity among all tested samples. These results suggest that cultivar genetic background may be a primary determinant of both aroma metabolites and TPS bioactivity, providing a theoretical basis for cultivar selection and quality optimization in oolong tea production.