Europium (Eu) doped LiF crystals have been grown by the Edge-defined film fed growth (EFG) technique. The designing and installation of the furnace used for the growth of the crystals have been discussed in detail. In the present study, Eu (Eu2O3) has been doped in LiF in different concentration (0.02–0.2 wt %). X-ray diffractometry (XRD) and Energy Dispersive X-ray (EDX) spectroscopy confirms the incorporation of Eu in LiF. The influence of Eu on LiF has been investigated through photoluminescence (PL), thermoluminescence (TL) and electron paramagnetic resonance (EPR) in as-grown and annealed crystals. PL emission spectra shows the presence of both Eu3+ and Eu2+ form in the as-grown crystals which is confirmed by EPR results. Whereas, in annealed crystals, Eu is present predominantly as Eu2+ form. This suggests that growing crystals at high temperature (∼900 °C) in argon gas atmosphere through EFG technique favours the reduction of Eu3+ → Eu2+. This reduction phenomenon has been explained on the basis of charge compensation model. TL study of the LiF: Eu (0.02–0.2 wt %) crystals has been done after irradiation with Co60 gamma rays. In this study, it has been observed that the TL intensity as well as glow curve structure of LiF: Eu crystals are a strong function of Eu concentration. The maximum TL is observed at Eu concentration of 0.05 wt% at which a well defined glow curve structure with a prominent peak at 185 °C and a small peak at 253 °C. Beyond this concentration (0.05 wt %), TL intensity decreases due to aggregation of defects in the host. The peak at 185 °C in LiF: Eu (0.05 wt %) is certainly due to the presence of Eu2+ associated defects which is also supported by the PL spectra. It has been observed that Eu doping have a key role in creation of more defect levels which lead to the increased number of electron and hole traps. Further, trapping parameters are analysed using glow curve deconvolution method to have an insight study of TL phenomena. Further, TL glow curve structure of as-grown and annealed crystal are distinct which may be attributed to the nature of defect traps formed inside the LiF. © 2018 Elsevier Ltd