Distillers’ grains has high potential in methane production but the process is affected by the acidification in anaerobic digestion. To enhance the methane production in solid-state anaerobic digestion, distillers’ grains was co-digested with cattle manure in different proportions in this study. Compared to distillers’ grains, cattle manure performed lower biodegradability but higher alkalinity and nutrients, hence relieved acidification and drove microbial succession for methane enhancement in the co-digestion with distillers’ grains. The highest increase in total methane yield (10.67%) was observed in the co-digestion of distillers’ grains and cattle manure at the proportion of 70:30 (T3). This was the synergistic action of reduced acidification, relatively high biodegradability of feedstocks, and balanced composition of hydrolytic bacteria, syntrophic bacteria and acetoclastic methanogens. Further analysis revealed the positive effects of indigenous microorganisms derived from distillers’ grains and cattle manure in methane enhancement. The enrichment of Sedimentibacter, Desulfitibacter, Tepidanaerobacter from distiller's grains, and Eubacterium, Methanoculleus, Methanobacterium, Methanobrevibacter mainly from cattle manure synergistically promoted organics conversion and methane production in T3. This study further affirmed the potential use of distillers’ grains in solid-state anaerobic digestion and provided a favorable strategy for its better methane production.