A series of orange–red light-emitting Sm3+ activated Ba2ScNbO6 (x = 0.03, 0.05, 0.08, 0.10, 0.12, 0.14, and 0.16) phosphors were prepared through a traditional high temperature solid-state method. The properties of the samples were characterized by X-ray diffraction and scanning electron microscope. The emission and excitation spectrum, concentration quenching mechanism, and fluorescence attenuation of the phosphors were also investigated in detail. Upon excitation with near-Ultraviolent (407 nm), the emission spectra are composed of 564 nm, 598 nm and 645 nm emission peaks, corresponding to the different transitions of Sm3+ ions 4G5/2 → 6HJ (J = 5/2, 7/2, and 9/2), respectively. The strongest emission at 598 nm comes from the 4G5/2 → 6H7/2 transition of Sm3+, which produces bright orange–red emission. The optimum doping concentration of Sm3+ ion in Ba2ScNbO6 is 8 mol% and the critical transfer distance (Rc) of Sm3+ was calculated to be 20.97A. The thermal stability of Ba2ScNbO6:Sm3+ phosphor was tested by temperature-dependent emission spectroscopy. In addition, the Commission International deL’Eclairage the chromaticity coordinate of Ba2ScNbO6:0.08Sm3+ phosphor is (0.5435, 0.4514), which located in the orange reddish region. All the results show that the Ba2ScNbO6:xSm3+ phosphors can be used as orange–red light-emitting material for white light-emitting diodes.