In this study, complementary metabolomic and proteomic analyses were conducted on the solar- and indoor-withered oolong tea leaves, and freshly plucked leaves as the control, for the purpose to reveal the mechanisms underlying the initial formation of some flavor determinants during the early stage of oolong tea processing. As a result, a total of 978 non-volatile compounds and 152 volatile compounds were identified, the flavonoids and several esters were differently accumulated in various tea samples. In total, 7048 proteins were qualitatively and quantitatively determined, the analysis on pathway enrichment showed that phenylpropanoid, flavonoid metabolisms, and protein processing in endoplasmic reticulum were the major pathways discriminating the different tea samples. The joint protein–metabolite analysis showed that the multiple stresses such as dehydration, heat, and ultra-violet irradiation occurred during the withering step induced the dynamic and distinct changes in the biochemical network in the treated leaves compared to fresh leaves. The significant decreases in flavonoids, xanthine alkaloids, and several amino acids contributed to the alleviation of bitter or astringent taste of withered leaves, although the decomposition of L-theanine resulted in the loss of umami flavor over the solar-withering step. Moreover, the fruity or floral aromas, especially volatile terpenoids and phenylpropanoids/benzenoids, were retained or accumulated in the solar withered leaves, potentially aiding the formation of a better characteristic flavor of oolong tea made by indoor withered tea leaves. Distinct effects of solar- and indoor-withering methods on the flavor determinant formation provide a novel insight into the relationship between the metabolite accumulation and flavor formation during the withering step of oolong tea production.

• Glutamic acid serves as a critical metabolism hub for diverse stress responses. • Long-term setting is conducive to the accumulation of key flavoring compounds. • Reduction in bitter/astringent components contributed to the mellow/rich flavor.