Thermally deposited 200 nm polycrystalline films of lithium fluoride (LiF) grown on glass substrates were irradiated with 150 MeV Ag ions at various fluences between 1× 10 11 and 2× 10 13 ions cm− 2. The irradiation induced structural and optical modifications were studied using glancing angle x-ray diffraction (GAXRD), optical absorption and photoluminescence (PL) spectroscopy. The GAXRD results show that the films are polycrystalline and the average grain size (estimated from the widths of the GAXRD peak using the Scherrer formula) decreases systematically from 46.3 nm for the pristine sample to 18.3 nm for the sample irradiated at a fluence of 3× 10 12 ions cm− 2. Thereafter, it remains constant. This reduction is attributed to strain induced fragmentation of grains. The optical absorption studies show dominant absorption bands of F 3 (385 nm) and F 2 (445 nm) colour centres. It is observed that the concentration of the colour centres increases with ion fluence and gets saturated at higher fluences. This can be correlated with GAXRD results in the sense that as the density of grain boundaries increases the concentration of colour centres also increases. The variation with fluence in PL intensities of the F 2 and colour centres is studied. The intensity of both bands (F 2 and) increases up to a fluence of 1× 10 12 ions cm− 2, followed by an exponential decrease, which is due to the increase in the non-radiative transition rate in the presence of defect-rich material.