Display omitted •TWGCe glasses show amorphous nature and are free from impurities and bubbles.•TWGCe glasses enhance optical properties of Ce3+ by reducing non-radiative losses.•Exhibit deep-blue luminescence through Ce3+: 5d → 4f transition when excited at 323 nm.•They are favourable as blue light sources in the design of phosphor-based white LEDs. Different concentrations of Ce3+-doped TeO2-WO3-GeO2-Ce2O3 (TWGCe) glasses were prepared by melt-quenching method and characterized. Different spectroscopic and luminescence properties were evaluated using room temperature absorption and emission spectra. The absence of sharp X-ray diffraction peaks and the presence of broad band from 18° to 35° shows the amorphous phase of studied glasses. The Fourier transform infrared absorption spectra show the presence of various vibrational bonds. The optical properties of TWGCe glasses were studied by exciting the glass samples at 323 nm ultraviolet wavelength. The quenching in luminescence is noticed at ×  = 0.5 mol% along with a red-shift at higher Ce3+ concentrations. The decay time was found decrease with increase of concentration of Ce3+ ions. These glasses emit intense blue luminescence with CIE coordinates (0.161, 0.018) when excited at 323 nm radiation. These glasses are favourable as blue light sources in the design of phosphor-based white LEDs.