This study presents the synthesis of samarium-substituted Ba-Ca hexaferrites (Ba0.5Ca0.5Fe12-xSmxO19) utilizing the sol–gel method. X-ray diffraction (XRD) analysis is performed to evaluate the structure of fabricated materials. The lattice shows an expansion up to a doping concentration of x = 0.12, and minor contraction at x = 0.16. Both X-ray density and bulk density exhibit an upward trend with increasing doping levels, while porosity reduces and dislocation density shows an increase. Scanning electron microscopy (SEM) confirms the homogeneity and uniformity of the doped samples. The dielectric properties displays the interaction of the materials with an external electric field, revealing that the dielectric constant (ε′), dielectric loss (ε″), and dissipation factor progressively increases with samarium concentration. Magnetic characterizations demonstrate a significant enhancement in saturation magnetization and coercivity, attaining peak values of 33.19 emu/g and 1.805 kOe, respectively. Moreover, the anisotropy field (Ha) and anisotropy constant (K) shows an increase with higher doping concentrations confirming the prepared material as an alternative for electric and magnetic industry applications.