A couple of novel ceramic luminescent materials based on Bi4(TiO4)3 and LiZnVO4 matrices have been developed by a conventional solid-state reaction method. An intense blue emission at 480 nm has been measured with an excitation at 418 nm from the Bismuth Titanate Bi4(TiO4)3 ceramic powder. A bright green emission at 533 nm has been measured upon with λ exci = 359 nm. The mechanisms involved in the observance of such prominent visible color emissions from these ceramic powders have been explained. Along side the measurement of their luminescence spectra, structural details of these ceramic powders have been carried out based on the recorded profiles of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier-transform IR spectroscopy (FTIR), and Raman spectra. With regard to thermal properties of these novel optical materials, their comprehensive differential thermo gravimetric analysis (TG–DTA) has also been undertaken and the important and interesting results are thus reported here.