Anaerobic digestion (AD) performance and microbial dynamics were investigated in a high-solid anaerobic digestion (HSAD) system of the organic fraction of municipal solid waste (OFMSW). 1, 5, 10, and 15% (w/w, dry weight of the OFMSW) of granular activated carbon (GAC) and zerovalent iron (ZVI) were added to the HSAD system. The results showed that adding ZVI and GAC can improve the methane yield of the OFMSW. Notably, R-(GAC + ZVI) exhibited the highest cumulative methane yield of 343.0 mL/gVS, which was 57.1% higher than that of the R-control. At the genus level, the dominant bacteria included norank_f__norank_o__MBA03, norank_f__norank_o__norank_c__norank_p__Firmicutes, Fastidiosipila, norank_f__Rikenellaceae, and Sphaerochaeta, while Methanoculleus, Methanobacterium, and Methanosarcina were the dominant archaea. The highest relative abundance of norank_f__norank_o__norank_c__norank_p__Firmicutes was 30.8% for the R-(GAC + ZVI), which was 71.4% higher than that of the R-control. The relative abundance of Methanoculleus and Methanobacterium for the R-(GAC + ZVI) and the R-control group accounted for 79.0 and 90.8% of the total archaeal abundance, respectively. Additionally, the relative abundance of Methanosarcina was 10.6% for R-(GAC + ZVI), which was higher than that of the R-control (1.1%). After the addition of GAC and ZVI, the electron transfer capacity of the HSAD system was enhanced, resulting in promoted methane production. Thus, the simultaneous addition of GAC and ZVI to the HSAD system can be an effective strategy to promote the cumulative methane yield of the OFMSW.