Sodium europium double tungstate [NaEu(WO 4) 2] phosphor was prepared by the solid-state reaction method. Its crystal structure, photoluminescence properties and thermal quenching characteristics were investigated aiming at the potential application in the field of white light-emitting diodes (LEDs). The influences of Sm doping on the photoluminescence properties of this phosphor were also studied. It is found that this phosphor can be effectively excited by 394 or 464 nm light, which nicely match the output wavelengths of near-ultraviolet (UV) or blue LED chips. Under 394 or 464 nm light excitation, this phosphor exhibits stronger emission intensity than the Y 2O 2S:Eu 3+ or Eu 2+-activated sulfide phosphor. The introduction of Sm 3+ ions can broaden the excitation peaks at 394 and 464 nm of the NaEu(WO 4) 2 phosphor and significantly enhance its relative luminance under 400 and 460 nm LEDs excitation. Furthermore, the relative luminance of NaEu(WO 4) 2 phosphor shows a superior thermal stability compared with the commercially used sulfide or oxysulfide phosphor, and make it a promising red phosphor for solid-state lighting devices based on near-UV or blue LED chips.