This electrolysis proceeds more efficiently when the electrolyte contains a few percent of LiF, possibly because it facilitates formation of an Li-C-F interface on the carbon electrodes.

Because of the large band gap for LiF, its crystals are transparent to short wavelength ultraviolet radiation, more so than any other material.

It is also used as a means to record ionizing radiation exposure from gamma rays, beta particles, and neutrons (indirectly, using the 63Li (n,alpha) nuclear reaction) in thermoluminescent dosimeters.

Lithium fluoride is widely used in PLED and OLED as a coupling layer to enhance electron injection.

[9] Naturally occurring lithium fluoride is known as the extremely rare mineral griceite.