We report an electrochemical reactor that converts 3.0 M KHCO3 into methane at the cathode, and oxidizes water at the anode. The molar ratio of methane product to unreacted CO2 gas (defined herein as “methane yield”) was measured to be 34% at a partial current density of 120 mA cm−2. The highest previously reported CO2-to-methane yield is 3%. Our reactor achieved this improvement in methane yield because it is fed with 3.0 M KHCO3, a type of reactive carbon solution, rather than gaseous CO2. The reactor uses H+ delivered by a bipolar membrane to form CO2 at the cathode. This CO2 is subsequently reduced into methane. A cationic surfactant added to the catholyte suppressed hydrogen evolution and increased methane formation. A 1D continuum model confirmed that H+ from the membrane promotes the formation of methane over multicarbon products at the cathode. These findings present design principles for electrochemical methane synthesis.