In this paper, the phase equilibria of LiF-BaF 2 and LiF-EuF 3 systems under short-annealed and slow-cooled conditions have been explained. In these two systems, LiBaF 3 and LiEuF 4 exist as the line compounds in the respective systems under the present experimental conditions. The thermally stimulated luminescence (TSL) properties of EuF 3 doped LiBaF 3 compositions are investigated after irradiation with γ-ray. A typical glow peak at 390K is observed in these samples, intensity of which increases up to 0.5mol% of Eu 3+ doping and then decreases due to concentration quenching. An intense glow peak at 540K observed only in 1.0mol% doped sample. Spectral studies of the TSL glows confirm Eu 3+ ions as the luminescent centers.