The Eu-doped SiO2-B2O3-NaF glass was prepared by sol-gel process, using tetraethoxy Silicane, boric acid and sodium fluoride as starting materials, 0.10 mol·L-1 EuCl3 solution as the dopant. The luminescent properties of Eu3+ doped SiO2-B2O3-NaF phosphors were investigated. The phosphors showed prominent luminescence in pink, the strong emission of Eu3+ comes from electronic transition of 5D0-7F1(591 nm)and 5D0-7F2(615 nm),which derived from two transition modes of magnetic-dipole and electric-dipole .The peak intensity of 591nm in SiO2-B2O3-NaF matrix is much stronger than it in the other matrixes, it means that SiO2-B2O3-NaF has sensitization on the transition of 5D0-7F1 (Eu3+). If there are broad bonds in the range of 275~380 nm in the excitation spectrum of Eu3+ -doped SiO2-B2O3-NaF glass, the emission peak intensity should be intensified. It is because the electron migration CT band of O2--Eu3+. For all Eu3+ concentrations used, the investigation found that when the mass of fraction got to 29.19×10-3, the luminescence intensity reached the summit. And there is a phenomenon of concentration quenching. Investigation with the same concentration of Eu3+ at different annealed temperature, we found that the sample annealed at 400 ℃, the luminescence intensity achieved its maximum value, and Eu3+ in this matrix had a phenomenon of temperature quenching. The structural characterization of these luminescent materials was carried by used XRD and TEM. The result showed that the phosphor was in amorphous phase.