The lack of electron donors is one of the key factors hindering hexanoic acid production from anaerobic fermentation. In this study, three different types of lactic acids were supplemented as exogenous electron donors to the anaerobic fermentation system of Chinese cabbage waste (CCW). The yields of hexanoic acid in the reactors supplemented with CCW lactic acid pre-fermentation broth (PFB), lactic acid diluent (LAD) and chemical lactic acid (LA) were 6996.8 mg COD/L, 4534.8 mg COD/L and 6777.1 mg COD/L, respectively. Compared with the reactor supplemented with LA, the electron efficiency of hexanoic acid in reactor supplemented with PFB increased by 188 %. Supplementing PFB shifted the microbial communities towards a direction favorable to hydrolysis and chain elongation, thereby facilitating the synthesis of hexanoic acid.