In order to explore the effect of secondary-fermentation technologies on the flavor quality of Zunyi characteristic pickled peppers， the secondary-fermented Zunyi characteristic pickled pepper was taken as the research object. Gas chromatography-mass spectrometry (GC-MS) combined with relative odor activity value (ROAV)， cluster analysis (CA)， and orthogonal partial least squares discriminant analysis(OPLS-DA) were used to explore the changes of volatile flavor compounds in the fermentation process of pickled peppers produced by secondary -fermentation method. The results showed that 42， 53， 62， 68 kinds of volatile flavor compounds were detected in 4 samples(fresh， traditional natural one- fermentation for 30 days， secondary-fermentation， and traditional natural one-fermentation for 150 days)， The relative contents of alcohols in pickled peppers after natural fermentation for 30 days and 150 days were 57.550% and 56.605%， respectively， and the proportion of flavor substances such as linalool， ethyl acetate， and acetic acid was relatively high. The proportion of esters， hydrocarbons， and acids was 29.838%， 22.202%， and 11.684%， among which methyl salicylate， 2-methyltetradecane， nonal， and other flavor substances accounted for more， and the flavor difference was obvious. Multivariate statistical analysis showed that the characteristic flavor components of different samples were statistically different， among which there were 12， 17， 20， and 16 kinds of key flavor substances with ROAV≥1， respectively. The volatile flavor differences of different pickled pepper samples could be further distinguished by CA and OPLS-DA. Among them， linalool， isoamyl alcohol， nonanal， tetradecane aldehyde， 2-undecane， acetic acid， methyl salicylate， ethyl acetate， 2-methyltridecane， and 2-methoxy-3-isobutylpyrazine could be used as key flavor substances to distinguish pickled peppers at different fermentation stages. Compared with the traditional natural fermentation， the flavor quality of the pickled peppers with Zunyi characteristics produced by the secondary-fermentation method was better， which could provide a basis for further research on the flavor formation mechanism of pickled peppers in the two-fermentation method and guide the precise regulation of flavor quality.