Herein, we report the successful electrochemical fluorination and defluorination of schafarzikite‐type compounds with the composition Fe0.5 m 0.5Sb2O4 (M=Mg or Co). We show that electrochemical methods can present a more controllable and less environmentally damaging route for fluorinating compounds in contrast to traditional methods that involve heating samples in F2‐rich atmospheres. The reactivity of the host lattices with fluoride during electrochemical fluorination makes this material an interesting candidate for fluoride‐ion battery applications. However, deleterious side reactions with the conductive carbon matrix during fluorination suggests to the contrary. Regardless of the side reactions, the schafarzikite structure was found to be an alternative reversible host lattice for fluoride incorporation and removal in addition to the previously reported Ruddlesden–Popper‐type compounds.