The influence of various annealing treatments on radioluminescent (RL) and thermoluminescent (TL) spectra of LiF:Mg,Cu,Si and LiF:Mg,Cu,P was investigated. The TL and RL emission bands for LiF:Mg,Cu,P are not the same; however, the emission band peaking at ∼383 nm is predominant in the TL and RL emission for LiF:Mg,Cu,Si. With the increase in annealing temperatures in the range of 240-300°C, for LiF:Mg,Cu,P, the intensity of TL decreases much more rapidly than that of RL. For LiF:Mg,Cu,Si, the area ratios of the two bands of RL and TL remain constant within experimental errors. It suggests that there is a significant decrease in the concentration of recombination centres in LiF:Mg,Cu,P after the annealing, in addition to the decrease in trapping centres, the recombination centres for main TL emission and RL emission in LiF:Mg,Cu,Si are the same, and the recombination centres for TL emission and RL emission in LiF:Mg,Cu,P are not the same. P is a more effective dopant than Si.