In this study, a series of barium titanate ceramics of the chemical composition BaTiO3 was prepared. The solid-state reaction route was adopted to synthesize the ceramic samples at various sintering temperatures of 1100–1300 °C. X-ray diffraction and FTIR spectroscopy were utilized to examine the structure of the fabricated ceramics. The UV–Vis–reflectance data were recorded to guess the optical bandgap energy of the synthesized ceramics. The ability of the synthesized ceramics to attenuate ionizing radiation was qualified using a Monte Carlo simulation (MCNP code) in the γ-energy interval ranging between 59 keV and 1408 keV. Shielding parameters, including LAC, TF, and RPE, were evaluated. The XRD and FTIR analyses showed the formation of a tetragonal BaTiO3 perovskite structure with the Pmmm space group. The crystallite size and the relative density increased, whereas the porosity decreased, with increasing sintering temperatures. Optical bandgap energy (Eg) values decreased as the sintering temperatures increased. The radiation shielding results depicted that raising the sintering temperature between 1100 °C and 1300 °C resulted in a slight increase in the µ values by a factor of ≈8 %. The mentioned increase in the µ values caused a reduction in the Δeq and Δ0.5, and TF values for the fabricated BaTiO3 ceramic samples, while the RPE values increased with increasing sintering temperatures between 1100 °C and 1300 °C.