NaBaPO4:Eu2+/Tb3+ phosphors were synthesized by the hydrothermal process. The phase structure of obtained samples was characterized by powder X-ray diffraction. The morphology and size were obtained by field emission scanning electron microscope. Under the excitation at 346 nm, NaBaPO4:Eu2+/Tb3+ phosphors exhibited the emission band originating from the 4f65d1 → 4f7 transitions of Eu2+ and the emission bands originating from the 5D4 → 7Fj transitions of Tb3+. The intensities and lifetimes of Eu2+ decrease with increasing Tb3+ concentrations. On the basis of luminescence properties of NaBaPO4:Eu2+/Tb3+ phosphors, we can conclude the energy transfer occurs between Eu2+ and Tb3+ in NaBaPO4 host.