By means of dielectric permittivity, electric modulus and impedance, the dielectric properties of LiF single crystals were investigated in the temperature range of 30°C-800°C and frequency range of 50 Hz-10 MHz. Two thermally activated relaxations, R1 and R2, were observed. The relaxation R1 showing activation energy around 0.8 eV was found to be related to the Li-ion diffusion in the crystal. The relaxation R2 contains three Arrhenius segments, the low-, mid-, and high-T segments, separated by boundary temperatures of 325°C and 425°C. These segments in the order of ascending temperature were found to be associated with F 3 , F 3