This study aims to synthesize of new type of nanocomposites based on polyvinyl alcohol(PVA)-polyvinyl pyrrolidone(PVP) bend doped with cerium oxide(CeO2) nanoparticles to apply in various photonics and energy storage fields. The structural, optical, and electrical features of PVA/PVP/CeO2 nanocomposites were examined. The results indicated that the optical absorption of PVA/PVP blend enhanced of 94.9% when the CeO2 NPs concentration reached of 3 wt.% at wavelength of 260 nm. The energy gap of PVA/PVP blend decreased of 54.2% with rising CeO2 NPs concentration to 3 wt.%. The other factors of optical properties enhanced with increasing CeO2 NPs concentration. The electrical properties were investigated in frequency ranging from100 Hz to 5 MHz. The results showed that the dielectric constant and electrical conductivity are improved of 12.3% and 66%, respectively, at frequency of 1 kHz with rising CeO2 NPs concentration to 3 wt.%. The elaborated optical and electrical improvements of the PVA/PVP blend would definitely introduce the PVA/PVP/CeO2 nanocomposites as precious UV-shielding materials for a wide set of optoelectronics industry. The PVA/PVP/CeO2 nanocomposites included excellent UV-absorption, low energy gap, and good physical and chemical properties compared with other nanocomposites.