Samarium doped pyrovanadate Ba2V2O7:Sm3+ phosphors were synthesized by traditional high-temperature solid-state reactionmethod. The phase and the structure of the samples were characterized by powder X-ray diffraction (XRD), and the luminescentproperties and the energy transfer mechanism of the material were investigated using quantitative photoluminescence (PL) spectroscopy.The excitation spectrum of the sample exhibited a broad ultraviolet (UV) band with maximum at around 341 nm due to V–Ocharge transfer transition of the host. The emission spectrum displayed a yellow-greenish broadband (peaking at around 498 nm)coming from the host Ba2V2O7 and three narrow peaks (at 561, 599 and 646 nm) attributed to the dopant Sm3+ ions. The PL spectrarevealed the energy transfer from the host to the Sm3+ ions. In addition, the color coordinates and the color temperature of the phosphorBa1.95V2O7:5%Sm3+ were (0.314, 0.365) and 6135 K, respectively, under 365 nm excitation, suggesting it to be a candidate ofsingle-phase converting phosphors for white-light-emitting diodes (WLEDs) with near-UV chips.