In recent years, inorganic multifunctional ferroelectric ceramics have been widely utilized in various fields, including aerospace, optical communication, and capacitors, owing to their high stability, easy synthesis, and flexibility. Rare-earth doped ferroelectric materials hold immense potential as a new type of inorganic multifunctional material. This work focuses on the synthesis of x%Sm ³⁺-doped 0.94Bi _0.5Na _0.5TiO ₃-0.06BaTiO ₃(BNTBT: x%Sm ³⁺in short) ceramics by using the conventional solid-state sintering method, aiming to comprehensively investigate their ferroelectric, energy storage, and photoluminescence (PL) properties. The X-ray diffraction analysis reveals that the introduction of Sm ³⁺does not trigger off the appearing of secondary phases or changing of the original perovskite structure. The scanning electron microscope (SEM) images demonstrate that Sm ³⁺incorporation effectively restrains the grain growth in BNTBT, resulting in the average grain size decreasing from 1.16 to 0.95 μm. The reduction in remanent polarization ( P _r) and coercive field ( E _c) can be attributed to both the grain size refinement and the formation of morphotropic phase boundaries (MPBs). Under an applied field of 60 kV/cm, the maximum value of energy storage density ( W _rec) reaches to 0.27 J/cm ³at an Sm ³⁺doping concentration of 0.6%. The energy storage efficiency ( η) gradually declines with electric field increasing and stabilizes at approximately 45% for Sm ³⁺doping concentrations exceeding 0.6%. This result can be ascribed to the decrease in Δ P( P _max – P _r) due to the growth of ferroelectric domains as the electric field increases. Additionally, all Sm ³⁺-doped BNTBT ceramics exhibit outstanding PL performance upon being excited with near-ultraviolet (NUV) light at 408 nm, without peak position shifting. The PL intensity peaks when the Sm ³⁺doping concentration is 1.0%, with a relative change (Δ I/I) reaching to 700% at 701 nm ( ⁴G _5/2→ ⁶H _11/2). However, the relative change in PL intensity is minimum at 562 nm ( ⁴G _5/2→ ⁶H _5/2) due to the fact that the ⁴G _5/2→ ⁶H _5/2transition represents a magnetic dipole transition, and the PL intensity remains relatively stable despite variations in the crystal field environment surrounding Sm ³⁺. Our successful synthesis of this novel ceramic material, endowed with both energy storage and PL properties, offers a promising avenue for developing inorganic multifunctional materials. The Sm ³⁺-doped BNTBT ceramics hold considerable potential applications in optical memory and multifunctional capacitors.