Highly transparent Ce3+, Tb3+ co-doped sodium silicate glasses were prepared by melt-quenching technique. The luminescent properties of Ce3+, Tb3+ single-doped and co-doped glasses, energy transfer process from Ce3+ to Tb3+ were systemically investigated through excitation spectra, emission spectra, decay curves, and energy level diagram. Tuning the content of Tb3+ can generate the varied hues from blue to white and eventually to yellowish green. Our results suggest that Ce3+, Tb3+ co-doped sodium silicate glasses could be used as converting phosphors for Near-ultraviolet LED chips to generate W-LEDs.