Laocong Shuixian (LCSX), a premium Wuyi rock tea derived from aged Shuixian tea trees, is valued by consumers for its distinctive “Cong flavor”—a unique aroma profile characterized by woody, bamboo leaf, and glutinous rice notes. However, the chemical basis and underlying mechanisms of this unique aroma remain unclear. Here, we assessed and established a professional sensory evaluation panel using the PanelCheck software, with significant F-value levels >5% confirming the panel’s discriminative capacity for key “Cong flavor” attributes. Combining a literature review and sensory analysis, we identified the descriptive terms associated with the “Cong flavor” of LCSX. Gas chromatography–olfactometry–mass spectrometry (GC–O–MS) analysis revealed 36 key aroma-active compounds, among which theaspirone (OAV = 500.05, ACI = 37%, Rwoody = 0.82), δ-decalactone (OAV = 65.6, ACI = 4.3%, Rwoody = 0.77), and 2-acetylpyrrole (OAV = 163, ACI = 9%, Rrice = 0.74) were identified as the contributors to the woody and rice-like notes of LCSX based on odor activity values and correlation analyses. Molecular docking results demonstrated that these compounds spontaneously bind to multiple olfactory receptors, with binding affinity ≤−5.0 kcal/mol, providing insights into their roles in human aroma perception: theaspirone to OR8D1; δ-decalactone to OR1E2, OR5M3, OR7D4, OR7G1, OR8D1 and OR8G1; and 2-acetylpyrrole to OR1E2, OR1G1, OR5M3, OR7D4, OR7G1, OR8D1, and OR8G1. This study enhances our understanding of the formation of distinctive aroma qualities in oolong tea and establishes a foundation for further research into its sensory and chemical properties.