We report the improved energy storage density and efficiency after 2.5% of Samarium substitution in ferroelectric Pb[(Mg1/3Nb2/3)0.80Ti0.20]O3 (PMNT) electroceramic. The microstructure and surface morphology were analyzed and correlated with various functional properties. The energy storage density, leakage current density, ferroelectric and dielectric properties were investigated thoroughly, indicating that Samarium's substitution significantly modified the microstructure, the dielectric strength, breakdown electric field, and turned ferroelectric PMNT to relaxor ferroelectrics. Due to the relaxor nature, the gap between remanent polarization and maximum polarization increases with the substitution of Samarium in PMNT matrix, which further increases the recoverable energy storage density and energy efficiency. A nearly 100% increase in recoverable energy density and efficiency was obtained at an electric field strength of 35 kV/cm at room temperature (∼296 K). The electroceramic shows maximum energy density near the ferroelectric phase transition temperature (325 K–345 K) region and provides a moderate energy storage density for possible applications in power microelectronics.