At present, high-solids anaerobic digestion of sewage sludge has drawn great attention due to the superiority of its small land area footprint and low energy consumption. However, a high organic loading rate may cause acids accumulation and ammonia inhibition, thus leading to an inhibited pseudo-steady state in which electron transfer through interspecies hydrogen transfer (IHT) between acetogens and methanogens is blocked. In this study, adding 50 mg/g TS (total solid) magnetite clearly reduced the accumulation of short-chain fatty acids and accelerated methane production by 26.6%. As demonstrated, the individual processes of anaerobic digestion could not be improved by magnetite when methanogenesis was interrupted. Analyzing stable carbon isotopes and investigating the methanogenesis pathways using acetate and H2/CO2 as substrates together proved that direct interspecies electron transfer (DIET) was enhanced by magnetite. Metatranscriptomic analysis and determination of key enzymes showed that IHT could be partially substituted by enhanced DIET, and acetate-dependent methanogenesis was improved after the blockage of electron transfer was scavenged. Additionally, the expression of both pili and c-type cytochromes was found to decrease, indicating that magnetite could replace their roles for efficient electron transfer between acetogens and methanogens; thus, a robust chain of electron transfer was established.