© 2020 Elsevier Ltd Anaerobic digestion of primary sludge with different additives, namely nano magnetite, graphite powder, activated carbon powder and NiCl2/CoCl2, were evaluated by biomethane potential tests, kinetics modelling and microbial community analysis. Specific methane yields increased from 136 mL/g VS for primary sludge to 146 mL/g VS, 151 mL/g VS, and 152 mL/g VS for the addition of nano magnetite, graphite powder, and activated carbon powder at optimal dosages, respectively. The first order hydrolysis constant kh increased from 0.488 d-1 to 0.526 d-1, 0.622 d-1, and 0.724 d-1, respectively. Microbial community analysis revealed that the abundance of key bacterial and archaeal populations was positively correlated with hydrolysis and methane production. The enhanced methane production with activated carbon powder was due to shifting methane formation pathway from acetoclastic to hydrogenotrophic methanogenesis. In contrast, nano magnetite and graphite powder additives enhanced the direct interspecies electron transfer evidenced by increased abundance of Methanosaeta and Methanolinea.