Photoluminescence (PL) and thermoluminescence (TL) measurements of LiF:Mg, Ti (DTG-4) single crystals, previously gamma irradiated with 500 Gy and thermally treated, were performed. The behaviour of the Mg centres, related to the known 5.5 eV optical absorption band, PL emission after repeated heating cycles with a heating rate of 1 K/s up to 373-653 K indicate that these centres are created simultaneously with the destruction of TL peaks. The decay of the PL emission after repeated heating cycles followed by 10 min annealing at 643 K coincides with the decreasing of the TL sensitisation factors of peaks 2, 3 and 5. Both these facts support the point of view that the precursors of the 5.5 eV centres act as competitive traps during TL readout. The behaviour of the Ti-related PL emission was found to be unexpectedly complex. Noticeable change of the Ti band shape and ambiguous behaviour of the Ti emission during subsequent heating indicate the possible presence of an additional Ti band. © 2001 Elsevier Science Ltd.