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The luminescence and scintillation properties of LiF:W were investigated in comparison with those of LiCaAlF6:Eu and GS20 (Ce-doped lithium silicate glass). LiF:W showed photoluminescence and scintillation emission peaking at the wavelength of 440 nm with the decay time of approximately 43 μs, which was shorter than those of LiCaAlF6:Eu and GS20. The light yield of LiF:W estimated by pulse height spectroscopy was approximately 90 photons/neutron.