In this paper, the effects of different storage years on the composition and content of flavonoids, antioxidant activity, and volatile components of Laoxianghuang (bergamot) were studied to provide theoretical support for the quality formation and age identification of Laoxianghuang. Five different storage years (one year, two years, four years, six years, and eight years) of Laoxianghuang were selected, and high-performance liquid chromatography (HPLC) was used to explore the composition of flavonoids. DPPH method, ABTS method, and ferric reducing/antioxidant power (FRAP) were used to evaluate the antioxidant activity in vitro, and gas chromatography-mass spectrometry (GC-MS) was used for qualitative and quantitative analysis of volatile components. Results showed that with the increase in storage years, the antioxidant properties of Laoxianghuang, such as total phenols, total flavonoids, DPPH free radicals, ABTS cationic radicals, and FRAP, all showed an upward trend. Compared with the one-year storage, the total phenolic and total flavonoid contents of Laoxianghuang after eight years of storage increased by 345.28% and 68.35%, respectively. The antioxidant properties of DPPH free radicals, ABTS cationic radicals, and FRAP increased by 75.19%, 58.97%, and 148.39%, respectively. Among the flavonoids, the contents of chlorogenic acid, ferulic acid, and catechin increased with the years and were positively correlated with the total phenols, total flavonoids, and antioxidant properties of Laoxianghuang. Among the volatile compounds, with the prolongation of storage time, the contents of terpenes and aromatic hydrocarbons such as limonene and 1-methyl-4-(1-methylethyl)-benzene in Laoxianghuang decreased. With the increase of alcohols, such as ethanol and α-terpineol, the smell became mellow. To sum up, with the prolongation of storage time, the content of total phenols and total flavonoids of Laoxianghuang increased, the antioxidant capacity enhanced, and the odor gradually became mellow, which could provide a scientific basis for the “ageing is better” of Laoxianghuang.
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