The Ce3+ ion-doped Na2ZnP2O7 and Na4P2O7 pyrophosphate phosphors were prepared for the first time via wet chemical method in the history of phosphors. We focused our studies on photoluminescence property of these inorganic solids. In addition, their structural, morphological, spectroscopic, and thermoluminescence properties were also systematically studied and well analyzed. The emission spectra of Ce3+ ion-doped Na2ZnP2O7 and Na4P2O7 phosphors show a broad band in the ultra violet (UV) spectral region due to the presence of 4f–5d transitions of Ce3+ ions. The interesting luminescence properties of these phosphors can make them to be attractive candidates for the application in various fields of luminescence. We reported that at higher concentration of cerium, the cluster formation increases due to ion interaction leading to quenching of the Ce3+ fluorescence. Their XRD was studied for testing the phase purity and crystallinity. SEM gives the particles of a quadrate shape with an average diameter of 1–5 µm, which suggests that the phosphors can be used to fabricate the solid-lighting devices. FT-IR spectra of these pyrophosphates give information regarding the internal and external modes of P2O74−group and metal–oxygen vibrations. Thermoluminescence property of only Na4P2O7 phosphor using γ-irradiated by 60Co source was reported, whereas Na2ZnP2O7 phosphor was found unfavorable in showing TL behavior. Numbers of solid phosphate materials have been synthesized and many still remain to be discovered. They are generally long-lasting, safe, and have a varied range of definite and potential materials applications.