Methanol synthesized from renewable hydrogen and captured CO2 has recently attracted great interest as a sustainable energy carrier for large-scale renewable energy storage. In this study, molten carbonate fuel cell’s performance was investigated with the direct conversion of methanol into syngas inside the anode chamber of the cell. The internal reforming of methanol may significantly improve system efficiency since the heat generated from the electrochemical reaction can be used directly for the endothermic reforming reaction. The porous Ni-10 wt%Cr anode was sufficient for the methanol steam reforming reaction under the fuel cell operating condition. The direct supply of methanol into the anode chamber resulted in somewhat lower cell performance, especially at high current density. Recycling of the product gas into the anode gas inlet significantly improved the cell performance. The analysis based on material balance revealed that, with increasing current density and gas recycling ratio, the methanol steam reforming reaction rate likewise increased. A methanol conversion more significant than 90% was achieved with gas recycling. The results showed the feasibility of electricity and syngas co-production using the molten carbonate fuel cell. Further research is needed to optimize the fuel cell operating conditions for simultaneous production of electricity and syngas, considering both material and energy balances in the fuel cell.