The effects of pH on the production of volatile fatty acids (VFAs) and the evolution of microbial community structure were studied via anaerobic fermentation of Chinese cabbage waste. The results showed that the concentration of total VFAs was highest at 20,241.4 mg COD/L at pH 6.0, followed by pH 7.0. Ethanol, acetate and butyrate were dominant under the acidic condition. The main products at pH 7.0 were acetate, propionate, and butyrate. Ethanol, acetate and butyrate were rapidly produced during the initial stage. The hexanoate concentration increased quickly from day 6 due to the chain extension between ethanol and butyrate, and was 4,885.1 mg COD/L on day 8, accounting for 30.4% of the total VFAs. As fermentation was extended, Bacteroidia and Clostridia were dominant at pH 6.0 and the uncontrolled pH, respectively. Clostridium IV, Ruminococcus, and Candida, were suspected to be related to hexanoate production.