Catechin, a natural antiglycative agent, was incorporated into fermented vinegar, and has high potential to lower the risk of diabetes. In this study, vinegar containing 5% catechin as a substrate for acetous fermentation significantly inhibited the formation of total fluorescent advanced glycation end-products (AGEs), as well as Nε-(carboxymethyl)lysine (CML)/Nε-(carboxyethyl)lysine (CEL), especially when added during acetic fermentation. Further study proved that catechin could not only significantly suppress the increase of blood glucose levels, but also inhibit α-amylase, α-glucosidase and β-glucosidase strongly with IC50 values of 0.533 mg mL-1, 0.307 mg mL-1 and 0.413 mg mL-1, respectively. Moreover, 32 volatile compounds were finally identified by headspace solid phase microextraction gas chromatography-mass spectrometry (HSPM-GC-MS) and electronic nose. The flavor of the catechin-vinegars, which possess relatively high ester and low acid contents, was superior to that of traditional vinegar. Therefore, it was helpful to use catechin as a functional food ingredient in vinegar to prevent AGE-associated diseases and alleviate postprandial hyperglycemia, through limiting the digestion of starch and inhibiting the uptake of glucose. Meanwhile, the pleasant flavor and safety of catechin-vinegar were better than traditional vinegar, which represents prominent value to attract consumers.