Baojing Huangjincha 1 green tea (HJC) is characterized by a fresh floral aroma with a distinctive milky note, setting it apart from both conventional and other novel green tea varieties. However, the key odorants contributing to this unique profile have not yet been fully identified. In this study, 109 common volatile compounds were detected from 22 HJC samples using comprehensive two-dimensional gas chromatography coupled with quadrupole time-of-flight mass spectrometry (GC × GC-QTOFMS). Headspace solid-phase microextraction combined with gas chromatography-olfactometry (HS-SPME-GC-O) and aroma extract dilution analysis (AEDA) were employed to identify 28 aroma-active compounds (FD ≥ 8), 18 (OAV ≥ 1) of which were quantified in the tea infusion. The accuracy of these results was validated by an aroma recombination model that closely replicated the original aromatic profile of HJC. Omission and addition experiments further revealed six critical odorants as pivotal contributors to the overall aroma, including geraniol, linalool, heptanal, 2-methylbutyraldehyde, hexanal, and phenylethyl alcohol. Moreover, molecular docking analysis indicated that phenethyl alcohol, linalool, and geraniol form stable conformations with olfactory receptors OR1A1 and OR5M3, facilitated by van der Waals forces, hydrogen bonds, and hydrophobic interactions. These findings provide a foundational theoretical framework for optimizing green tea processing techniques and enhancing quality control standards.