Dy3+-doped Li8Bi2(MoO4)7 (LBM: Dy3+) white-emitting phosphors have been prepared by sol-gel method at about 400 similar to 550 degrees C low temperature. The electronic structure of Li8Bi2(MoO4)7 is also calculated using density functional theory. The calculation results show that Li8Bi2(MoO4)7 has a direct band gap with 2.63 eV, the top of the valence band and the bottom of the conduction band are dominated by O 2p and Mo 4d, respectively. The effect from Bi3+ ions is so weak that it could be neglected, which is also be proved by the experimental results. The crystal structure and luminescent properties of the obtained phosphors are characterized by powder X-ray diffraction and photoluminescence spectrum, respectively. Photoluminescence results showed that the obtained phosphors can be excited efficiently by near-UV 387nm and generated white light emission. The yellow/blue ratio and Commission International de I'Eclairage color coordinates could be tuned by adjusting the concentration of Dy3+. Results demonstrated that Li8Bi2(MoO4)7: Dy3+ was a potential white light-emitting phosphor candidate for NUV-based w-LEDs.