In this study, the effects of different sun withering degrees (75% (CK), 69% (S69), 66% (S66), 63% (S63), and 60% (S60) water content in the withered leaves) on black tea sensory quality were investigated by means of sensory evaluation plus metabolomics analysis. Sensory evaluation results showed higher sensory quality scores for the black tea in S69–S66, due to better freshness, sweeter taste, and a sweet and even floral and fruity aroma. Additionally, 65 non-volatile components were identified using Ultra Performance Liquid Chromatography-Quadrupole-Time of Flight-Mass Spectrometry (UPLC-Q-TOF/MS). Among them, the content increase of amino acids and theaflavins was found to promote the freshness and sweetness of black tea. The aroma of tea was analyzed using combined Solvent Assisted Flavor Evaporation-Gas Chromatography-Mass Spectrometry (SAFE-GC-MS) and Headspace-Solid Phase Micro Extract-Gas Chromatography-Mass Spectrometry (HS-SPME-GC-MS), and 180 volatiles were identified, including 38 variable importance in projection (VIP) > 1 (p< 0.05) and 25 Odor Activity Value (OAV) > 1 volatiles. Statistical analysis revealed 11 volatiles as potential major aroma differential metabolites in black tea with a different sun withering degree, such as volatile terpenoids (linalool, geraniol, (E)-citral, and β-myrcene), amino-acid-derived volatiles (benzeneethanol, benzeneacetaldehyde, and methyl salicylate), carotenoid-derived volatiles (jasmone and β-damascenone), and fatty-acid-derived volatiles ((Z)-3-hexen-1-ol and (E)-2-hexenal). Among them, volatile terpenoids and amino acid derived volatiles mainly contributed to the floral and fruity aroma quality of sun-withered black tea.