Polycrystal of GdPO4:RE3+(RE=Tb, Tm) phosphors were prepared by solid- state method. Vacuum ultraviolet excitation and emission spectrum and the energy transfer mechanism between the host and dopants of Tb3+ and Tm3+ were investigated respectively. The emission of Gd3+ at 313 nm was enhanced by the strong absorption of CTS of Tm3+ at 180 nm in GdPO4: Tm. It has also been concluded that the excitation of Gd3+ is transferred to Tb3+ and then emission peaks of 5DJ→7FJ of T b3 + were observed.