Undoped and rare earth (RE = Ce, Dy, and Eu) doped GdCa4O(BO3)(3) phosphors were synthesized by solid-state diffusion technique. Formation of the sample was confirmed by taking X-ray diffraction (XRD) pattern of the sample. Photoluminescence (PL) emission spectrum showed characteristic emission of RE doped in the GdCa4O(BO3)(3) sample. It is observed that doping of RE ion initially enhanced the TL yield, attained an optimum TL for a particular concentration of dopant (i.e., 0.5 mol%) then decreased with further increase in dopant concentration for all the samples. We found that Ce is the best activator for enhancing the TL yield in GdCa4O(BO3)(3) system. Fading of TL intensity of the sample was studied and it is found that fading of the TL is about 5% over the period of 15 days. The simple glow curve, linear response to gamma-ray dose and less fading; makes the GdCa4O(BO3)(3):Ce(0.5 mol%) phosphors a suitable candidate for TL dosimetry.