The blue thermoluminescence (TL) emission of different thermally annealed (i) β-eucryptite (LiAlSiO4), (ii) virgilite-petalite (LiAlSi5O12) and (iii) virgilite-petalite-bikitaite (LiAlSi10O22) mixed crystals have been studied. The observed changes in the TL glow curves could be linked to simultaneous processes taking place in the lithium aluminosilicate lattice structure (phase transitions, consecutive breaking linking of bonds, alkali self-diffusion, redox reactions, etc). The stability of the TL signal after four months of storage performed at RT under red light, shows big differences between annealed (12 hours at 1200ºC) and non-annealed samples. The fading process in non-annealed samples can be fitted to a first-order decay mathematical expression; however preheated samples could not be reasonably fitted due to the highly dispersion detected. The changes observed in the X-ray diffractograms are in the intensity of the peaks that denote modifications in the degree of crystallinity and, in addition, there are some differences in the appeareance of new peaks that could suppose new phases (e.g. β-spodumene).