The flavour of white tea can be influenced by the season in which the fresh leaves are picked. In this study, the sensory evaluation results indicated that spring-picked white tea (SPWT) was stronger than autumn-picked white tea (APWT) in terms of the taste of umami, smoothness, astringency, and thickness as well as the aromas of flower and fresh. To explore key factors of sensory differences, a combination of biochemical composition determination, widely targeted volatilomics (WTV) analysis, multivariate statistical analysis, and odour activity value (OAV) analysis was employed. The phytochemical analysis showed that the free amino acid, tea polyphenol, and caffeine contents of SPWTs were significantly higher than those of APWTs, which may explain the higher umami, smoothness, thickness, and astringency scores of SPWTs than those of APWTs. The sabinene, (2E, 4E)-2, 4-octadienal, (-)-cis-rose oxide, caramel furanone, trans-rose oxide, and rose oxide contents were significantly higher in SPWTs than in APWTs, which may result in stronger flowery, fresh, and sweet aromas in SPWTs than in APWTs. Among these, (2E,4E)-2,4-octadienal and (-)-cis-rose oxide can be identified as key volatiles. This study provides an objective and accurate basis for classifying SPWTs and APWTs at the metabolite level.