In this work, the sol–gel combustion method was used to fabricate a series of rare earth samarium doped Ca-hexaferrites (CaFe12-xSmxO19). X-ray diffraction was used to explore the structural insights. The structural analysis confirmed the magnetoplumbite phase throughout all compositions with the expansion in the lattice. Furthermore, microstructural analysis showed an increase in X-ray density and a decrease in porosity and dislocation density with increasing doping levels, respectively. Morphology confirmed the uniform distribution of particles throughout all the fabricated samples. The crystallite size was determined from X-ray diffraction data and ranges between 48.28–55.52 nm. Magnetic parameters such as remanence and saturation magnetization showed an increase from 25.27 emu/g to 44.029 emu/g, while coercivity values dropped from 3.301 kOe to 2.334 kOe causing significant deviations in the magnetic moment per formula unit μB (mB), Anisotropy field (Ha), and anisotropy parameter (B). The materials were shown to have promising magnetic characteristics for storage applications.