The metal ions Li+, Na+ and Al3+ co-doped BaF2∶Eu3+ phosphors were synthesized by the high temperature solid state reaction. The microstructure, morphologies and luminescent properties were characterized by X-ray diffraction, scanning electron microscopy, photoluminescence spectroscopy and fluorescence decay curves, respectively. The experimental results show that the emission intensity at 611 nm of Li+, Na+, Al3+ doped with 9% doping concentration is increased by 4.71 times, 1.51 times and 1.35 times respectively at 266 nm excitation, compared with the single doped 23% Eu3+ sample. After the incorporation of Li+ or Al3+, the lifetime of 5D0 level of Eu3+ becomes longer, and the incorporation of Na+ shortens the energy level life of Eu3+. Compared with BaF2∶23%Eu3+ sample, the luminescence intensities of 9% Li+, 6%Na+, 23%Eu3+ co-doped BaF2 sample and 9% Li+, 12% Al3+, 23%Eu3+ co-doped BaF2 sample increased by 1.73 times and 3.05 times respectively, and the corresponding energy level life was increased.