The polycrystalline samples of 0.8BiSmxFe[Formula: see text]O3–0.2PbTiO3 ([Formula: see text] and 0.20) were prepared by using the conventional solid-state reaction technique and sintered at high temperature (850[Formula: see text]C). X-ray diffraction (XRD) confirms the distorted rhombohedral crystal structure for all the composites at room temperature. The surface morphology was checked by field-emission scanning electron microscope (FESEM) technique and homogeneous mixing of the components was confirmed by energy-dispersive analysis of X-ray (EDAX). The detailed study of dielectric properties of the composites reveals an increasing nature of dielectric constant ([Formula: see text]) and loss tangent (tan[Formula: see text]) with the increase of temperature due to thermal activation. The Arrhenius plots of temperature dependence of AC conductivity yield the activation energy within the material at high-temperature range. The ferroelectric study shows that the remnant polarization decreases with the increase of Samarium (Sm) concentration.