In this study, the metabolism of methanol and changes in an archaeal community were examined in a bioelectrochemical anaerobic digestion sequencing batch reactor with a copper-coated graphite cathode (BEAD-SBRCu). Copper-coated graphite cathode produced methanol from food waste. The BEAD-SBRCu showed higher methanol removal and methane production than those of the anaerobic digestion (AD)-SBR. The methane production and pH of the BEAD-SBRCu were stable even under a high organic loading rate (OLR). The hydrogenotrophic methanogens increased from 32.2 to 60.0%, and the hydrogen-dependent methylotrophic methanogens increased from 19.5 to 37.7% in the bulk of BEAD-SBRCu at high OLR. Where methanol was directly injected as a single substrate into the BEAD-SBRCu, the main metabolism of methane production was hydrogenotrophic methanogenesis using carbon dioxide and hydrogen released by the oxidation of methanol on the anode through bioelectrochemical reactions.