In this paper, some results of the study on the roles of the dopants in the LiF:Mg,Cu,Na,Si thermoluminescent (TL) material that was developed at the Korea Atomic Energy Research Institute for radiation protection are presented. Although there have been many studies to investigate the roles of the dopants in LiF:Mg,Cu,P TL material in the TL process, there are some discrepancies in the understanding of the roles of Cu and P between various researchers. In case of LiF:Mg,Cu,Na,Si TL material, there are a few studies on the roles of the dopants. Three kinds of samples in each of which one dopant is excluded, and the optimised sample, were prepared for this study. The measurements and analysis of the three-dimensional TL spectra, based on the temperature, wavelength and intensity, and the glow curves for those samples are used in this study. The results show that Mg plays a role in the trapping of the charge carriers and Cu plays a role in the luminescence recombination process; however, the effect of Na and Si on the glow curve structure and the TL emission spectra is much less than that of Mg and Cu. It is considered that Na and Si each plays a role in the improvement of the luminescence efficiency.