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 <i>x</i>%Sm<sup>3+</sup>-doped 0.94Bi<sub>0.5</sub>Na<sub>0.5</sub>TiO<sub>3</sub>-0.06BaTiO<sub>3</sub> (BNTBT:<i>x</i>%Sm<sup>3+</sup> 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<sup>3+</sup> 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<sup>3+</sup> 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 (<i>P</i><sub>r</sub>) and coercive field (<i>E</i><sub>c</sub>) 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 (<i>W</i><sub>rec</sub>) reaches to 0.27 J/cm<sup>3</sup> at an Sm<sup>3+</sup> doping concentration of 0.6%. The energy storage efficiency (<i>η</i>) gradually declines with electric field increasing and stabilizes at approximately 45% for Sm<sup>3+</sup> doping concentrations exceeding 0.6%. This result can be ascribed to the decrease in Δ<i>P</i> (<i>P</i><sub>max</sub><sub> </sub>– <i>P</i><sub>r</sub>) due to the growth of ferroelectric domains as the electric field increases. Additionally, all Sm<sup>3+</sup>-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<sup>3+</sup> doping concentration is 1.0%, with a relative change (Δ<i>I/I</i>) reaching to 700% at 701 nm (<sup>4</sup>G<sub>5/2</sub>→<sup>6</sup>H<sub>11/2</sub>). However, the relative change in PL intensity is minimum at 562 nm (<sup>4</sup>G<sub>5/2</sub>→<sup>6</sup>H<sub>5/2</sub>) due to the fact that the <sup>4</sup>G<sub>5/2</sub>→<sup>6</sup>H<sub>5/2</sub> transition represents a magnetic dipole transition, and the PL intensity remains relatively stable despite variations in the crystal field environment surrounding Sm<sup>3+</sup>. 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<sup>3+</sup>-doped BNTBT ceramics hold considerable potential applications in optical memory and multifunctional capacitors.