Zha-Chili samples prepared from natural fermentation using three different types of food ingredients were used as study objects, and the volatile components of Zha-Chili at different fermentation times were isolated and identified using simultaneous distillation extraction-gas chromatography/mass spectrometry (SDE-GC/MS). . The effects of different food ingredients and fermentation times on the volatile components of Zha-Chili were compared and flavor substances were analyzed by principal component analysis. The results showed that the largest numbers of different volatile components were in the Zha-Chili samples prepared with taro-corn and corn after 45 days of fermentation (87 and 90, respectively). The main volatile components of Zha-Chili prepared with corn were esters alkanes and acids, while those prepared with taro-corn were esters alkanes and alcohols. The highest number of different volatile components after 90 days of fermentation was observed in Zha-Chili prepared with rice (82); the main volatile components were esters, alkanes, and olefins. The relative content of esters were highest in the Zha-Chili samples prepared with corn, taro-corn, and rice, with values of 40.69–47.25%, 64.41–74.35%, and 60.29–67.29%, respectively. According to the changes in the relative content and types of volatiles in the fermentation process, as well as the principal component scores of Zha-Chili samples after fermentation, the best fermentation time for Zha-Chili prepared with taro-corn and corn was 45 days and that for Zha-Chili prepared with rice was 45–90 days. These results indicate that the flavor formation of Zha-Chili can be affected by the inclusion of different starch raw materials during fermentation.