New lead-cerium phosphate glasses in the system xCeO2(50-x)PbO-50P2O5 were successfully prepared by the melt-quenching process. The amorphous and/or crystalline character of the as prepared compositions were confirmed by both X-ray powder diffraction (XRD) and electron diffraction patterns (EDP) related to transmission electron microscopy (TEM). The surface morphology and the analytical amounts of glasses constituents have been studied by scanning electron microscopy (SEM) equipped with Energy-dispersive X-ray spectroscopy (EDX) apparatus. It was found that P2O5 as a host network can dissolve extremely high concentration from CeO2 without crystallization of the host glass network. Some cerium phosphate (CeP2O6) clusters can be formed and precipitated in the main amorphous network, particularly in glasses of high CeO2 contents ˃ 20 mol%. Formation of such type of clusters has an effective influence on enhancing material structure and properties, since the hardness number of the studied materials is highly enhanced. The chemical shift 31P NMR of glasses is improved toward increasing shielding process by the effect of CeO2 addition.