BaWO4:RE3+ (RE = Eu or Sm) phosphor powders were prepared with different doping concentrations of the activator ion by using the conventional solid-state reaction method. The dependences in the crystal structure, luminescence intensity, and morphology on the Eu3+ and the Sm3+ concentrations in BaWO4 were investigated using X-ray diffraction (XRD), photoluminescence spectrophotometry, and scanning electron microscopy (SEM), respectively. XRD analysis showed tetragonal BaWO4 structures for all the phosphors synthesized, regardless of the type and the doping concentration of the activator ion. SEM images indicated that as the concentration of activator ions was increased, the crystalline particles showed an increasing tendency to agglomerate irregularly. The room temperature excitation spectra of Eu3+- or Sm3+-doped BaWO4 phosphors consisted of a broad charge transfer band in the ultraviolet region and several sharp 4f-4f transitions. When Eu3+-doped BaWO4 phosphors were excited at 274 nm, the emission spectra exhibited sharp bands due to inner shell transitions occurring from the excited energy state 5D0 to the lower energy levels 7FJ (J = 1, 2, 3, and 4). For Sm3+-doped BaWO4 phosphors, three intense emission peaks at 568, 603, and 649 nm and a very weak line at 712 nm were observed. The highest asymmetry ratio-the intensity ratio of the 4G5/2 → 6H9/2 electric dipole to the 4G5/2 → 6H5/2 magnetic dipole transitions-was obtained for 1 mol% doping of Sm3+, indicating that the Sm3+ ions occupied the non-inversion symmetry sites.