Bismuth titanate (Bi4Ti3O12) (BiT), glass is prepared by the melt‐quench technique in the SiO2–K2O–Bi2O3–TiO2 (SKBT) system doping with Eu2O3 and transparent BiT glass‐ceramics (GC) is derived from it by controlled heat‐treatment at 500°C by varying duration. The structural properties of the heat‐treated GC are investigated using X‐ray diffraction (XRD), electron microscopy [Field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM)], and fourier transform infrared reflectance spectroscopy. FE‐SEM and TEM images show the formation of polycrystalline spherical particles of 100–200 nm with 10–15 nm crystallites after heat‐treatment. A significant increase in εr value (from 20 to 35) was observed with increase in heat‐treatment time. The transmission losses of GC which happened with heat‐treatment time are due to Rayleigh scattering exhibited by nanocrystallites of BiT. The excitation spectra have been recorded by monitoring emission at 612 nm corresponding to the 5D0 → 7F2 transition and an intense 467 nm excitation band corresponding to the 7F0 → 5D2 has been observed. Emission spectra were recorded by exciting the glass samples at 467 nm. It is observed that with increase in heat‐treatment time, the intensity of red emission at 612 nm increases by 8‐fold, which has happened due to the occupancy of Eu3+ ions in the low phonon energy crystal sites of BiT.