<p>A series of Sm³⁺ activated BaAl₂O₄ phosphors was effectively synthesized by a known combustion method. Structural and optical properties are investigated by using X-ray diffraction pattern (XRD), Fourier transform infrared (FTIR), and photoluminescence (PL) analysis. The XRD of the prepared sample exhibits that all the samples prepared are in a single phase and match with standard JCPDS no. 01–072-1331. The XRD pattern indicates a hexagonal structure. The FTIR spectra of the BaAl₂O₄ sample show the stretching vibrations of aluminum-oxygen, barium-oxygen, and barium-oxygen-aluminum bonds, confirming the presence of the BaAl₂O₄ structure. The luminescence properties are broadly investigated by recording their PL excitation and emission spectra. The BaAl₂O₄:Sm³⁺ phosphors show a strong absorption range in 340–420&#xa0;nm, which is well suited for application in LEDs. Under the excitation wavelength of 403&#xa0;nm, the BaAl₂O₄:Sm³⁺ phosphor emits yellow, orange, and red emissions along the Commission Internationale de l'Éclairage (CIE) chromaticity coordinates found at 565&#xa0;nm (0.408, 0.589), 603&#xa0;nm (0.640, 0.359), and 650&#xa0;nm (0.725, 0.274) (0.615). The optimal doping concentration of Sm³⁺ doped BaAl₂O₄ is at 1&#xa0;mol %. The concentration mechanism is studied, and this mechanism arises from the dipole–dipole interaction between Sm³⁺ ions. The results demonstrate that BaAl₂O₄:Sm³⁺ phosphors have the potential to function as red–orange phosphors for white LEDs.</p>