Multiferroic composites exhibit remarkable magnetoelectric (ME) characteristics, offering diverse applications. The study investigated samarium (Sm) doped composites, specifically (1 − x)Ba0.5Sm0.5TiO3–xCo0.5Sm0.5Fe2O4 (x = 0.0,0.02,0.04,0.06), formed by combining Sm doped BaTiO3 and CoFe2O4 using the solid-state reaction method. X-ray diffraction analysis revealed a tetragonal structure in Ba0.5Sm0.5TiO3 (SmBT) and a cubic spinel secondary phase in Co0.5Sm0.5Fe2O4 (SmCF), suggesting uniform distribution of grains. The optical bandgap in SmBT and the composite showed a slight decrease (from 3.14 eV to 3.01 eV) with increasing Sm concentration, as observed in optical studies. The dielectric measurements showed that the dielectric constant of SmBT was higher (ϵ′ = 526.3) between 80 Hz and 8 MHz, while the composites had a lower dielectric constant (ϵ′ = 438.4) at lower frequencies and the real part of dielectric was fitted by Havriliak–Negami (H–N) model shows that the dielectric curves exhibit a characteristic dispersion pattern known as the cole–cole mode (grains) also confirmed by cole–cole plot. The response exhibited linearity, adhering to the universal dielectric response model. Ferroelectric behaviour in the underlying material confirms SmBT non-centrosymmetric character and the storage efficiency (η) of all composites surpassed 90%, reaching a peak of 94.8% with a ferrite content of 0.02. The versatility of the Sm-doped composites offers opportunities for diverse applications in fields such as electronics, telecommunications, and biomedical devices. Notably, these materials can be utilized in Memory Devices, Actuators, and other relevant applications.