Cerium-doped Ca2Al2SiO7 phosphors were synthesized via the combustion technique and annealed at 1073 K, 1173 K, and 1373 K. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), photoluminescence (PL), and thermoluminescence (TL) studies were performed to explore the variation of structural, morphological, luminescence, and TL properties with annealing temperature. The XRD plot showed an increase in crystallinity with an increase in annealing temperature. Similarly, the enhancement of PL intensity with an increase in annealing temperature supports the increased crystallinity of the phosphor samples. Detailed analysis of traps and trap parameters was carried out using the principle of TL. Samples were irradiated with different γ-ray doses, and, on heating, luminescence was observed. Thus, TL glow curves were drawn and deconvoluted using computerized glow curve deconvolution (CGCD) and Chen's peak shape method to study the traps and trap parameters. With increasing annealing temperature, an increase in TL intensity was observed. Regardless of annealing temperature, every sample displayed a linear dose–response for doses ranging from 3 Gy to 500 Gy. TL investigations suggested that the produced phosphors are suitable candidates for gamma dosimetry applications. [ABSTRACT FROM AUTHOR]