Eu2+/Sm3+ co-doped silicate glass was prepared by high temperature melting under reducing atmosphere and the Eu2+/Sm3+ co-doped SrSiO3 transparent glass-ceramics were obtained after heat-treatment. X-ray diffraction (XRD) and Raman spectra confirmed the formation of SrSiO3 nano-crystals in the glass matrix. The photoluminescence excitation (PLE) spectra and photoluminescence (PL) spectra of the samples were measured. A broad emission band from 400 nm to 550 nm due to the 4f65d1 → 4f7 transitions of Eu2+ was observed, as well as several sharp emission peaks at 563 nm, 600 nm, 646 nm and 713 nm ascribed to the 4f → 4f transitions of Sm3+. The luminescence properties of the glass ceramics with different molar ratio of Eu2+/Sm3+ were studied and the corresponding chromaticity coordinates were calculated. The ultraviolet light-emitting diode (UV-LED) excitable glass-ceramics emitting white light were obtained by tuning the relative emission intensity of Eu2+ and Sm3+. The results indicate that the Eu2+/Sm3+ co-doped SrSiO3 transparent glass-ceramics can be used as a potential matrix material for White LED under UV-LED excitation.