In the coal biogasification, butyric acid is an important intermediate product. The enrichment of butyric acid-producing bacteria in coal geological methanogens is critical to confirm this assertion. Therefore, to study a method for enrichment of butyric acid-producing bacteria and to explore characteristic factors for evaluating the enrichment effect would be the basis for further strain isolation and metabolomics research. In this study, the nutrition control method was used for the butyric acid-producing bacteria enrichment from concentrated bacteria solution in Sihe coal seam. The characteristic factors' changes in gas production, gas composition, butyric acid concentration, and pH were observed and analyzed in the experiment. High-throughput sequencing was used as a verification method to validate the medium and genera enrichment effect that can be used for the butyric acid-producing bacteria. Through experimental research and analysis, it was identified that the glucose-sucrose-maltose medium was the beneficial medium to the enrichment of butyric acid-producing bacteria, and the high-throughput sequencing determined that the enriched genera wereClostridiumspp. Glucose-sucrose-maltose medium experimental data confirmed that the decrease of CO(2)and H(2)daily yield, the increase of butyric acid concentration, and the decrease of pH value had a significant positive correlation with the enrichment ofClostridiumspp.