A series of phosphor of MBPO7:Tm3+, and MBPO7:Tm3+, Gd3+ (M= Mg, Sr, Ca) were prepared and studied. The XRD data showed Tm3+, Gd3+ didn’t affects the lattice parameters. Excitation spectra exhibited high absorption in vacuum ultraviolet (VUV) region. There existed strong emission peaking at 453nm and 363nm correspond to the 1D2 →3HJ (J=4, 6) emission transition of Tm 3+ when excited under VUV. With the changes of cation in the samples, the excitation spectra changed greatly, and lead a great change in its emission spectra. The crystal lattice parameters affect the ratio of intensity of the peak at 454nm and 312nm.