To explore the effects of different withering methods on the quality of Congou black tea, this study focused on five different withering methods: natural withering, warm-air withering, sun–natural combined withering, sun withering, and shaking withering. Gas chromatography‒mass spectrometry (GC‒MS), high-performance liquid chromatography (HPLC), and ion-exchange chromatography techniques were used to analyze the nonvolatile and volatile components and composition of the tea. The results revealed significant differences (p < 0.05) in the contents of nonvolatile constituents including caffeine, polyphenols, soluble sugars, free amino acids and their components, theaflavins, thearubigins, and catechins among the five different withering methods, with varying degrees of correlation between these components. A total of 227 aroma compounds were detected, and significant differences in the contents of alcohols, aldehydes, and ketones were observed. A relative odor activity value (ROVA) analysis of the aroma compounds revealed that 19 compounds had an ROVA > 1. Among them, benzylaldehyde, trans-2-decenal, decanal, benzaldehyde, nonanal, hexanal, trans-linalool, and geraniol from the shaking withering method had significantly higher ROVA values than those from the other withering methods, which may be the reason for the prominent floral and fruity aroma of shaking withering. This study revealed the impact of different withering methods on the quality of Congou black tea, providing a scientific basis for the development of Congou black tea with different flavors and the improvement of Congou black tea processing techniques.