The recovery of methane from waste-activated sludge and rice straw often encounters challenges due to inefficient electron transfer between microorganisms. To break through this bottleneck, a novel and effective strategy is urgently needed. Here, we propose adding dual reaction centers (DRCs) catalyst with electron-rich and electron-poor microregions into the anaerobic digestion (AD) system. Pigeon manure was transformed into a novel DRCs catalyst, Fe-PMC, through pyrolysis and doping. Our findings indicate that the micro-electric field on the surface of Fe-PMC effectively aggregated humic acid-like substances and increased sludge conductivity. Compared to the control group (0 mg/L), adding trace amounts of Fe-PMC (40 mg/L) significantly increased methane production by 27.45%. High-throughput sequencing analyses revealed that Fe-PMC enhanced the relative abundance of functional microorganisms, such as Geobacter (23.62%) and Methanobacterium (35.53%), thereby promoting methanogenic co-metabolism. Furthermore, functional genes associated with carbon dioxide reduction to methane and direct interspecific electron transfer were upregulated by 3.41% to 297.66%. This study provides a valuable reference for recovering renewable energy from waste using DRCs catalysts.