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V 2 O 5 thin films were deposited on glass and p-type silicon substrates by radio frequency (RF) sputtering of a single V 2 O 5 target. Half of the samples were annealed at 500 °C at room ambient for an hour. The morphological, structural, and optical properties of the thin films were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV–Vis data. The results showed that while the as-grown V 2 O 5 thin films had smooth surfaces with an amorph phase, annealed films had rougher surfaces with grains in the polycrystalline phase. It is also reported that the band gap of V 2 O 5 thin films decreased from 2.47 to 2.37 eV. Furthermore, the electrical properties of Ag/V 2 O 5 /p-Si junctions were analyzed by current-voltage (I–V) measurements. It was presented that both Ag/V 2 O 5 /p-Si structures with as-grown and annealed V 2 O 5 thin films had exciting rectifying behaviors. It was observed that while the barrier heights of the rectifying junctions were nearly the same, the ideality factor and series resistance values of the Ag/V 2 O 5 /p-Si device fabricated by annealed V 2 O 5 thin film were higher than the device with as grown V 2 O 5 thin film. Finally, the photoelectrical properties of both samples were analyzed by I–V under various light intensities. It was seen that both Ag/V 2 O 5 /p-Si devices had exciting photosensing behavior. While the increase in reverse bias current values with the increase in light intensity was observed for both devices, it was seen that the device obtained by as-grown thin film had much more sensitivity to light. • The impact of annealing on RF-sputtered V 2 O 5 thin films was explored. • Enhanced crystal properties and tunable band gaps in annealed V 2 O 5 thin films were highlighted. • Intriguing rectifying behaviors in Ag/V 2 O 5 /p-Si heterojunctions were observed. • The high sensitivity of photoelectrical responses in Ag/V 2 O 5 /p-Si junctions were presented. [ABSTRACT FROM AUTHOR]