Abstract: The research of enhancing biomethanation of coal has been paid much attention, which is an effective measure for increasing coalbed methane production. Adding conductive material to the digestive system can effectively accelerate direct interspecific electron transfer and increase methane production, which has great potential in enhancing the anaerobic digestion of organic matter. In this study, long-flame coal was used as the substrate to construct an anaerobic digestion system. The effect of the addition of graphene on biomethane production was discussed from the aspects of cumulative methane yield, the changes of key intermediates in the liquid phase, the microbial community structure, the methane metabolic pathway, and the changes of surface functional groups in residual coal after anaerobic digestion. The results showed that adding 0.4 g/L of graphene to the anaerobic digestion system based on coal effectively enhanced the entire anaerobic digestion process, not only enhanced methane production, but also brought forward the peak of methane production. At the early stage of digestion, the activities of hydrolytic bacteria (Paraclostridium) and hydrogen-production and aceogenic microflora (Alcaligenes and Sphaerochaeta) were enhanced, and sufficient nutrients were accumulated in the early stage. At the peak of methane production, the abundance of Methanoculleus decreased while the abundance of Methanosarcina significantly increased after the addition of graphene. The β subunit and γδ subunit of acetyl-coa decarbonyase/synthase, as key enzymes in the acetic acid synthesis pathway, increased by 233.54% and 3.32%, respectively. This significantly increased the abundance of Methanosarcina and mainly produced methane in the form of acetic acid nutrition. The abundance of Geobacter and Anaerovorax bacteria that can use ethyl acetate increased, and the Geobacter with high abundance were likely to DIET with Methanosarcina by bioelectric connection assisted by graphene. This electron transport mode accelerated the formation of biomethane to some extent. The carbonyl carbon (C=O) and carboxyl carbon (COO—) on the surface of residual coal decreased by 42.8% and 49.5%, respectively, after the addition of graphene, indicating that graphene effectively promoted the degradation of coal by microflora. The addition of graphene improves the activity and degradation efficiency of microflora, speeds up the process of anaerobic digestion, provides abundant substrate for methanogenic microflora, and improves methane production.