An efficient approach of bioconverting the organic wastes in liquor wastewater (LW) and waste activated sludge (WAS) to valuable short-chain fatty acids (SCFAs) via anaerobic fermentation was explored. The maximal SCFAs concentration was 5400 mg COD/L with approximate 80.0% acetic and propionic acids under optimized conditions (LW/WAS ratio 1:1, pH 8 and fermentation 4 d). Mechanisms investigation found that the fermentation of LW/WAS made up the drawbacks of sole WAS fermentation by improving the bioavailable substrates and low C/N ratio to stimulate the microbial activities. The bioconversion efficiency of substrates for SCFAs generation was therefore enhanced. The humic acids present in LW could also play positive roles in SCFAs promotion. Moreover, the performance of LW/WAS fermentation was highly correlated with appropriate fermentation pH. The fermentative bacteria responsible for SCFAs production were highly enriched and the activities of key hydrolases, acid-forming enzymes and ATP concentration were greatly improved at pH 8.