The sintering process acquired ferromagnetic copper ferrite ceramic material with a small concentration of Ni ion at 1100 °C for 1 h. Previously, copper ferrite with Ni proportions powder was acquired by the wet chemical process according to the relation CuFe2-xNixO4 where x takes values 0.0, 0.015, 0.03, 0.04, and 0.05. The role of Ni ion in the copper ferrite structure was investigated by X-ray analysis, Scanning electron microscope, EDX analysis, and density measurements. The gamma-ray shielding properties for the fabricated CuFeNiO ceramics samples were evaluated using the Monte Carlo simulation method. The obtained results show an enhancement in the linear attenuation coefficient for the fabricated ceramics with increasing the insertions of Ni ions within the fabricated samples, where increasing the Ni ions concentration between 0 and 1.19 wt% increases the linear attenuation by between 1.581 and 1.771 cm−1 (at 0.103 MeV), 0.304–0.338 cm−1 (at 0.662 MeV), and 0.160–0.178 cm−1 (at 2.506 MeV), respectively. Simultaneously, the radiation protection efficiency for a 1 cm thickness of the fabricated samples increased between 14.8 and 16.3% with increasing the Ni ions between 0 and 1.19 wt%. Although the Ni doping concentration does not exceed 1.5 wt% of the total composition of the fabricated ceramics, the shielding capacity of the fabricated ceramics was enhanced by more than 11%, along the studied energy interval. Therefore, the fabricated samples can be used in gamma-ray shielding applications.