In this study, the structural, morphological, photoluminescence (PL), and dosimetric properties of Ca2-xAl2SiO7: xCr3+, at various Cr3+ concentrations (0 ≤ x ≤ 1 mol%) have been studied. The phosphor material was synthesized via sol-gel route with an octadecylamine as a catalyst. The average crystallite sizes were estimated to be in the range 21–30 nm using the modified Scherrer method which are in good agreement with data yielded by TEM micrographs. The energy-dispersive X-ray (EDX) spectra with scanning electron microscope (SEM) data confirm the homogeneous existence, and distribution of constituent elements within the structure and approved the sol-gel preparation method. PL spectra shows that Cr3+ doped Ca2Al2SiO7 structure has shoulder broadening and maximum peaks maintained at 442 ± 3.0 and 491 ± 3.02 nm upon 337 nm excitation which caused by 4F (4A2→4T2), 4F (4A2→4T1), and 4P (4A2→4T1) electronic spin-allowed transitions. Thermoluminescenc (TL) sensitivity characteristics of the obtained samples were scrutinized using Co-60 γ-radiation source. Cr0.4 sample was found to be optimum and its TL intensity increases linearly with increasing γ-doses from 0.5 up to 10 Gy. An accuracy using relative standard deviation (RSD) calculations of the homogenous study for Cr0.4 was found to be 4.02% (<10%, accepted due to ISO rules). Threshold dose of Cr0.4 sample was computed to be about 258 μGy. Acquired results of photon attenuation parameters estimations of Ca2Al2SiO7 composition using Phy-X PSD online program show that this composition is a bone equivalent dosimeter. According to this article, Cr0.4 doped Ca2Al2SiO7 sample can be considered as useful TL-material in various dosimetric applications.