Among transition metal oxides (WO₃ and MoO₃), vanadium oxides have garnered significant attention for their outstanding properties and diverse applications across various fields. For instance, vanadium pentoxide (V2O5) is known for its chemical sensing, photochromism, and catalytic properties, making it a suitable material for electronic information displays, electrochromic devices, optical--electrical switches, color memory devices, and more. Vanadium pentoxides (V2O5) have been already prepared by various methods. V₂O₅ is the most saturated (highest oxidation state) oxide and therefore the most stable one in the V–O system. It crystallizes with an orthorhombic unit cell structure belonging to the P_mnm space group . As materials with reduced dimensions often exhibit unique properties distinct from their bulk counterparts, recent efforts have focused on synthesizing nanostructures of vanadium oxides and studying their structure--property relationships. The V_2-4xCe_5xO₅ (0) nanoparticles were prepared using a solid-state technique. Depending on the X-ray diffraction analysis, the NPs crystallized in an orthorhombic structure of V_2-4xCe_5xO₅. A significant decrease in the crystallite size and band gap energy was observed. Eg was found to be 1.83 eV with Ce content. This is attributed to lattice expansion via Ce ions and the formation of oxygen vacancies within the bandgap. The absorption coefficient, optical transmission, and the complex refractive index were also determined. Substitution-doped V₂O₅ improved, allowing it to be useful for solar cells and optoelectronics.