Cassava alcohol wastewater (CAW) was utilized as a mixed feedstock to explore whether the addition of CAW could improve the anaerobic digestion of Molasses alcohol wastewater (MAW). The result showed that the rate of removal of the soluble chemical oxygen demand in the M treatment mixed with CAW was 70.13 ± 0.16%, which was significantly higher than that of the C treatment (only MAW), which was 61.23 ± 0.36%. Co-digestion in the M treatment resulted in higher methane production, achieving 23.89% increase in methane yield compared to C treatment. The addition of CAW helps to alleviate the accumulation of volatile fatty acids (397.06 ± 141.82 mg·L-1), enhance the stability of system and promote the establishment of stable and active microbial communities. Microbial community structure analysis indicated that hydrolytic bacteria such as Bacteroidetes, Firmicutes, and Proteobacteria, and acetoclastic methanogens, including Methanosaeta and Methanosarcina were more abundant in the co-digests.