Magnetic biochar is a potential economical anaerobic digestion (AD) additive. To better understand the possible role of magnetic biochar for the improvement of biomethanization performance and the retention of methanogens, magnetic biochar fabricated under different precursor concentrations were introduced into organic fraction of municipal solid waste (OFMSW) slurry AD system. Results showed that methane production in AD treatment with magnetic biochar fabricated under 3.2 g FeCl3:100 g rice-straw ratio increased by 11.69% compared with control treatment without biochar addition, due to selective enrichment of microorganisms participating in anaerobic digestion on magnetic biochar. AD treatment with magnetic biochar fabricated under 32 g FeCl3:100 g rice-straw ratio resulted in 38.34% decreasement of methane production because of the competition of iron oxide for electron. Furthermore, 25% of total methanogens were absorbed on magnetic biochar and can be harvested with magnet, which can offer a potential solution for preventing the methanogens loss in the anaerobic digesters.