Ion emission has been obtained from a LiF‐coated tungsten field‐emitter tip. Ion formation is thought to be caused by the high electric field experienced by the LiF. At the time of emission the electric field at the surface of the LiF is calculated to be on the order of 100 MV/cm. Inside the LiF the field is on the order of 10 MV/cm. These fields exceed the value needed to produce bulk dielectric breakdown in LiF. The surface field is of sufficient magnitude to produce ion emission by field evaporation from the crystal surface. Even prior to dielectric breakdown, precursor processes can lead to ion formation. Electric‐field‐stress fragmentation of the LiF layer is thought to occur, followed by ionization of the fragments.