MFA was first synthesized in 1896 by the Belgian chemist Frédéric Swarts by reacting methyl iodoacetate with silver fluoride. It can also be synthesized by reacting methyl chloroacetate with potassium fluoride
Because of its toxicity, MFA was studied for potential use as a chemical weapon during World War II. It was considered a good water poison since it is colorless and odorless and therefore it can toxify the water supply and kill a big part of the population. By the end of the war, several countries began to make methyl fluoroacetate to debilitate or kill the enemy.