In this study, we have synthesized CaF2:Nd3+,Ce3+ phosphors by solid state reaction method. The thermoluminescence (TL) properties of the family of synthesized phosphors (CaF2:Ce3+ and CaF2:Ce3+,Nd3+) were investigated using a combination of a SCHOTT BG39 and HC414/46 filters. This gave the highest TL intensity of each phosphor after 10 Gy β-irradiation. Two TL glow peaks of CaF2:Nd3+,Ce3+ phosphor are centered at around 90 and 265 °C (with a heating rate of 2 °Cs−1). The glow peaks displayed a linear dose response in the range of 0.1–50 Gy. Various heating rates (VHR) were performed between 0.5 and 10 °Cs−1. It was seen that the TL intensity at 90 °C decreases and peak maximum temperature shifts to higher temperatures with an increasing heating rate. The TL intensity of the glow peak located at 265 °C increases with heating rate. The initial rise (IR) applied after TM–Tstop experiment and computerized glow curve deconvolution (CGCD) methods in addition to the VHR method on the glow curves of CaF2:Nd3+,Ce3+ phosphor were used to determine the number of peaks, the order of kinetics (b), activation energy (E) and frequency factor (s). The response of TL glow curves remained constant within ±2% deviation from the initial value after 10 cycles of reuse.