The Na2SO4∶Tm3+ phosphor was synthesized by the high temperature solid state reaction method in air. The crystalline structure was examined by X-ray diffraction (XRD). Narrow bands observed in emission spectra were well identified with the electronic transitions within the 4f12 configurations of Tm3+, and the excitation spectrum is consisted of strong bands assigned to the 4f12→4f11 5d transition at 183 nm, the O2--Tm3+ charge transfer band at 170 nm and weak bands assigned to host absorption (130, 223 and 258 nm). In addition, the authors also found that the content of Tm3+ in the 8～16 mg concentration range caused quenching.