Studies were carried out to investigate the temperature dependence of OSL in LiCaAlF₆: Eu, Y phosphor (LCAF). The generic protocol and methodology for conducting such studies has been suggested. The material is investigated in the temperature range of 100–260 °C. The residual TL after various sequences is used as a probe to investigate the effectiveness of thermal and optical stimulation in releasing trapped charges. It is found that the simultaneous application of thermal and optical stimulation results in more efficient and faster depletion of signal in comparison to the sum of thermal and optical stimulations alone when carried out in isolation. Thus, simultaneous application of temperature and optical stimulation lead to increased synergistic effect in terms of acquisition of luminescence signal.