The rare earth Sm3+ doped (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 high-entropy phosphor (0~0.10 mol) were prepared by solid-state method. The study found that with the increase of Sm3+ concentration, the second phase of Sm2Ti2O7 gradually appeared in (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 high entropy powder, and its luminous intensity changed obviously. When the Sm3+ ions concentration was 0.04mol, a single perovskite structure of the (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 high-entropy powder had a single perovskite structure, and the components of each element were evenly distributed, and exhibited the best fluorescence performance. The (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 high-entropy phosphors showed the pure yellow light emission by doping Sm3+ ions. Under the excitation near ultraviolet light, the color coordinates of (0.515 9,0.471 5), the color temperature of 2 469 K, and the color purity of 83.0% for (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3-0.04Sm high-entroy phosphor were obtained. The results show that the (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 high-entropy phosphors have great potential applications in yellow phosphor for white LED.