The bioelectrochemical conversion of coal to methane was investigated in an anaerobic batch reactor containing yeast extract and activated carbon. In anaerobic degradation of coal, yeast extract was a good stimulant for the growth of anaerobic microorganisms, and activated carbon played a positive role. An electrostatic field of 0.67 V/cm significantly improved methane production from coal by promoting direct and mediated interspecies electron transfers between exoelectrogenic bacteria and electrotrophic methanogenic archaea. However, the accumulation of coal degradation intermediates gradually repressed the conversion of coal to methane, and the methane yield of coal was only 31.2 mL/g lignite, indicating that the intermediates were not completely converted to methane. By supplementing yeast extract and seed sludge into the anaerobic reactor, the intermediate residue could be further converted to methane under an electrostatic field of 0.67 V/cm, and the total methane yield of coal increased to 98.0 mL/g lignite. The repression of the intermediates to the conversion of coal to methane was a kind of irreversible substrate inhibition. The irreversible substrate inhibition in the conversion of coal to methane could be attenuated under the electrostatic field of 0.67 V/cm by ensuring sufficient biomass through biostimulation or bioaugmentation.