Effects of Optimized Key Processing Parameters on Macro-Compositions and Volatile Organic Compounds in High-Altitude Oolong Tea (Camellia sinensis (L.) O. Kuntze)

High-altitude environments provide a favorable basis for tea quality formation, but suitable processing parameters for high-altitude Oolong Tea (HAOT, Camellia sinensis (L.) O. Kuntze) remain unclear. This study optimized key processing parameters for HAOT using a three-factor, three-level orthogonal design involving withering method, shaking intensity and standing time. Sensory evaluation, quantitative descriptive analysis (QDA), macro-compositions determination, headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry (HS-SPME-GC-MS), multivariate statistics and correlation analysis were used to clarify quality differences and their chemical basis. Leaf anatomical observation showed that high-altitude fresh leaves had a thicker cuticle and more compact mesophyll structure, suggesting the need for targeted processing regulation. Range analysis indicated that shaking intensity had the largest R value for sensory scores, followed by withering method, whereas standing time showed a comparatively small R value. The favorable combination was combined withering, heavy shaking (6 rounds) and 60 min standing, hereafter referred to as FHM. FHM showed the highest floral and fruity aroma scores and produced a mellow, full-bodied taste with a sweet aftertaste. It also contained significantly higher flavonoid and soluble sugar levels than the other processing combinations. A total of 65 volatile organic compounds were detected, with terpenoids and esters as the dominant classes. ROAV analysis identified geraniol, linalool, β-ionone, (E)-nerolidol and benzaldehyde as representative major aroma-active compounds, while geraniol and linalool were especially prominent in FHM. Correlation analysis further linked flavonoids and soluble sugars with positive taste attributes, and linalool and geraniol with floral–fruity aroma. These results provide a practical basis for optimizing HAOT processing and improving product quality.