Biogas upgrading to biomethane with microbial electrosynthesis (MES) is receiving much attention due to increasing biomethane demands and surplus renewable energy. Research has demonstrated the feasibility of MES to increase methane yield by reducing CO2 in anaerobic digestion (AD). Such CO2 reduction occurs at the cathode and requires the supply of both protons and electrons. The most studied sources of protons and electrons are oxidation of organic substances and water, generated at the anode. These anodic reactions, however, also imply the production of CO2 and O2, respectively, both with negative implications for the AD process. A source of protons and electrons without CO2 and O2 as by-products would be beneficial for MES-enhanced biomethane production. This opinion article discusses the possibility of ammonium to serve as a sustainable proton and electron source.