Conventionally, the anaerobic digestion of industrial effluent to biogas constitutes less than 65% methane, which warrants its potential methanation to mitigate carbon dioxide and other anthropogenic gas emissions. The performance of the anaerobic digestion process can be enhanced by improving biochemical activities. The aim of this study was to examine the synergistic effect of the magnetite and bioelectrochemical systems (BES) on anaerobic digestion by comparing four digesters, namely a microbial fuel cell (MFC), microbial electrolysis cell (MEC), MEC with 1 g of magnetite nanoparticles (MECM), and a control digester with only sewage sludge (500 mL) and inoculum (300 mL). The MFC digester was equipped with zinc and copper electrodes including a 100 Ω resistor, whereas the MEC was supplied with 0.4 V on the electrodes. The MECM digester performed better as it improved microbial activity, increased the content of methane (by 43% compared to 41% of the control), and reduced contaminants (carbon oxygen demand, phosphates, colour, turbidity, total suspended solids, and total organic carbon) by more than 81.9%. Current density (jmax = 25.0 mA/m2) and electrical conductivity (275 µS/cm) were also high. The prospects of combining magnetite and bioelectrochemical systems seem very promising as they showed a great possibility for use in bioelectrochemical methane generation and wastewater treatment.