Demineralization is required in upgrading low-grade coal to serve as an alternative energy resource for the production of fuel and valuable chemicals but generates a large amount of low-grade coal wastewater (LCWW). The objective of this study was to investigate the effects of a co-substrate on an anaerobic membrane bioreactor (AnMBR) treating LCWW. CH4 was not produced during the operation fed by LCWW alone. When yeast wastes (YW) were supplemented, there was a gradual increase in the biodegradability of LCWW, achieving 182 CH4 mL/g COD with 58% COD removal efficiency. The analysis of physicochemical characteristics in the effluent of AnMBR, done by excitation-emission matrix (EEM) and size exclusion chromatography (SEC), showed that the proportion of soluble microbial products (SMPs) and aromatic group with high-molecular weight (>1 kDa) increased. Microbial analysis revealed that the increased dominance of bacteria Comamonas, Methanococcus, and Methanosarcina facilitated biodegradation of LCWW in the presence of YW.