Alkali bicarbonate is synthesized in an electrolytic cell from alkali carbonate. The electrolytic cell includes an alkali ion conductive membrane positioned between an anolyte compartment configured with an anode and a catholyte compartment configured with a cathode. The alkali conductive membrane selectively transports alkali ions and prevents the transport of anions produced in the catholyte compartment. An aqueous alkali carbonate solution is introduced into the anolyte compartment and electrolyzed at the anode to produce carbon dioxide and/or hydrogen ions which react with alkali carbonate to produce alkali bicarbonate. The alkali bicarbonate is recovered by filtration or other separation techniques. When the catholyte solution includes water, pure alkali hydroxide is produced. When the catholyte solution includes methanol, pure alkali methoxide is produced.