Lithium fluoride films were prepared by atomic layer deposition (ALD) using a new route in which LiN(SiMe₃)₂ is used as a precursor and SF₆ plasma as a coreactant. Conformal LiF films were deposited at 150 °C at a growth rate of ∼0.4 Å per cycle. All deposited films were polycrystalline and slightly lithium-rich with a composition of LiF_0.8, independently of the plasma conditions (e.g. exposure time, pressure and power). The levels of H, C, N, O, Si, and S were all <1 at%. Spectroscopic ellipsometry measurements were carried out over the wavelength range of 140–2480 nm and showed a refractive index of 1.37 at 633 nm for films deposited using 1 s plasma exposure time. We conclude that short plasma exposures are preferred, since a prolonged exposure time leads to an increase in optical absorption and lower growth per cycle values. Furthermore, mass spectrometry measurements revealed the formation of SiMe₃F species during both half-cycles, originating from the reaction between the precursor ligands and fluorine species present either at the surface or in the plasma. Moreover, the SF₆ plasma step led to the formation of fluorocarbon species, suggesting that dissociation and recombination in the plasma takes place. Overall, this work demonstrates that SF₆ plasma offers a promising alternative to other coreactants for ALD of high purity lithium fluoride.