<p>Transition metal oxides exhibit significant potential in photocatalytic applications. In the current research, a comprehensive determination of structural, optical, and electronic properties of V₂O₅ and TiO₂ nanomaterials was characterized using X-ray diffraction (XRD), field scanning electron microscopy (FESEM), and photoluminescence (PL) analysis. First-principles calculations were used to explore deeper insight into electronic band structures, density of states (DOS), light absorption, and optical conductivity. Exploration of theoretical and experimental results confirms that V₂O₅ exhibited an orthorhombic crystalline structure while TiO₂ crystallized in the anatase phase with energy bandgap 2.14 and 1.77&#xa0;eV respectively. DFT calculations related to the partial density of states (PDOS) reveal that electronic structures of V₂O₅ and TiO₂ facilitate better charge transfer due to the hybridization of V-3d, Ti-3d, and O-2p orbitals. Photoluminescence (PL) results revealed that PL intensity peaks of V₂O₅ and TiO₂ samples 3.0 × 10⁶ and 8.0 × 10⁴ (a.u.) at 713&#xa0;nm and 669&#xa0;nm respectively. DFT calculations related to light absorption α(ω) and optical conductivity reveal that 2.2 × 10⁵ cm⁻¹, 4.6 × 10⁵ cm^−1, and 3 Ω⁻¹cm⁻¹, 8 Ω⁻¹cm⁻¹ for V₂O₅ and TiO₂ respectively. These combined experimental and theoretical results reveal that TiO₂ demonstrated superior photocatalytic efficiency. This performance is attributed to its smaller energy bandgap, lower P.L intensity peaks, enhanced light absorption, and increased optical conductivity which contributes to enhanced (electron-hole) charge separation, and favorable band edge positions.</p>