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%Sm³⁺-doped 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ (BNTBT:x%Sm³⁺ 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 Sm³⁺ does not trigger off the appearing of secondary phases or changing of the original perovskite structure. The scanning electron microscope (SEM) images demonstrate that Sm³⁺ 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/cm³ at an Sm³⁺ doping concentration of 0.6%. The energy storage efficiency (η) gradually declines with electric field increasing and stabilizes at approximately 45% for Sm³⁺ doping concentrations exceeding 0.6%. This result can be ascribed to the decrease in ΔP (P_max – P_r) due to the growth of ferroelectric domains as the electric field increases. Additionally, all Sm³⁺-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 Sm³⁺ doping concentration is 1.0%, with a relative change (ΔI/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_5/2 transition represents a magnetic dipole transition, and the PL intensity remains relatively stable despite variations in the crystal field environment surrounding Sm³⁺. 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 Sm³⁺-doped BNTBT ceramics hold considerable potential applications in optical memory and multifunctional capacitors.