Nanostructures of calcium fluoride (CaF2) doped with Eu, Tb, Dy, Cu, and Ag were synthesized by the coprecipitation method and studied for their thermoluminescence (TL) and photoluminescence (PL) properties. The PL emission spectrum of pure CaF2nanostructure has a broad band in the 370–550 nm range. Similar spectra were observed in case of doped samples, beside extra bands related to these impurities. The maximum PL intensity was observed in Eu doped sample. The TL results of Eu, Cu, Ag, and Tb doped samples show weak glow peaks below 125°C, whereas Dy doped one is found to be highly sensitive with a prominent peak at 165°C. This sample was further exposed to a wide range of gamma rays exposures from137Cs source. The response curve is linear in the 100 Gy-10 kGy range. It is also observed that the particle size of CaF2nanostructure was significantly reduced by increasing Dy concentration. These results showed that Dy is a proper activator in the host of CaF2nanostructure, providing a highly sensitive dosimeter in a wide range of exposures and also plays a role as a controlling agent for particle size growth.