<p>Controlled synthesis of vanadium oxide (VO) with tailored nanostructures is crucial for optimizing their functional performance in catalytic and sensing application. Herein, we demonstrate a simple and effective temperature-regulated spray pyrolysis technique under short deposition time for preparing nanostructured VO films with appropriate microstructural and surface morphology. XRD analysis reveals a strong temperature- dependent evolution of crystallinity and phase composition, with well-crystallized and stable film obtained at 300&#xa0;°C exhibited α-V₂O₅ phase. XPS analyses shows that the crystallized films exhibit a dominant V⁵⁺ oxidation state with a minor contribution of V⁴⁺ species. SEM and AFM investigations show that film grown at 300&#xa0;°C develop a uniform vein-like network with textured ridge-like features, significantly enhancing surface reactivity and the availability of actives sites. Optical studies reveal a direct band gap of approximately 2.2&#xa0;eV with enhanced light absorption, while photoluminescence spectra confirm localized deep-level emissions associated with oxygen vacancy defect. Furthermore, film grown at 300&#xa0;°C exhibit a superior photoactivity toward Rhodamine B degradation compared to previous works, attributed to the synergistic effects of crystallinity, Vanadium-states, and specific surface area arising from the nanostructured morphology. This study highlights the critical role of temperature-controlled growth in vanadium oxide nanostructure formation and provides a scalable route toward the development of optimized VO-based materials for sensing and environmental applications.</p>