A series of Sm3+-doped 0.96Na0.5Bi0.5TiO3-0.04CaTiO3 (NBT-0.04CT∶xSm3+, 0.002≤x≤0.020) lead-free piezoelectric ceramics were prepared by a conventional solid-state reaction method. The phase structures of the samples were characterized by X-ray diffractometry, and all the samples show a single perovskite structure. The photoluminescence properties of the samples were measured by fluorescence spectrophotometer, and the samples show the strongest excitation peak at 479 nm, which matches well with the blue LED chip used in the white LED synthesis. The dominant emission peak is located at 597 nm (4G5/2→6H7/9), presenting strong orange-red luminescence. NBT-0.04CT∶0.010Sm3+ ceramics shows optimal luminescence performances among the Sm3+-doped NBT-0.04CT ceramics, and superior thermal stability of its luminous properties is achieved in the temperature range from 278 K to 473 K. The results indicate that NBT-0.04CT∶xSm3+ceramics have promising applications in white LED.