A new Eu2+/Sm3+ co-doped silicate glass was prepared,and its thermal stability and optical properties were studied. The intense blue (475 nm),yellow (562 nm),orange (599 nm) and red (644 and 706 nm) emissions were simultaneously observed at the room temperature under the excitation at 360 nm. The blue (475 nm) luminescence is due to the 4f65d1→4f7 transition of Eu2+,the yellow (562 nm) luminescence is due to the 4G5/2→6H5/2 transition of Sm3+,the orange (599 nm) luminescence is due to the 4G5/2→6H7/2 transition of Sm3+ and the red (644 and 706 nm) luminescence is due to the 4G5/2→6H9/2 and 4G5/2→6H11/2 transitions of Sm3+,respectively. With the increase of the concentration of Sm3+ ions,the hue of Eu2+/Sm3+ co-doped silicate glass varies gradually from greenish blue eventually to white. When the doped molar fraction of Eu2+ and Sm3+ ions are 0.05% and 1.0% respectively,the chromaticity coordinate of the glass is measured to be (0.312,0.307),which is close to the standard pure white (0.333,0.333). The results indicate that Eu2+/Sm3+ co-doped silicate glass is potential materials for white light-emitting diodes (WLED).