In the present work, we have fabricated a highly photo responsive Schottky barrier diode based on cerium infused vanadium pentoxide thin film (Ce-V2O5) as a interfacial layer. It was coated on a glass slide by low-cost sol-gel spin-coating technique and annealed at 500 °C. Structure, surface morphology, optical and electrical characteristic of Ce infused V2O5 films with different Ce concentrations viz 0, 2, 4 and 6 wt% were investigated. X-ray diffraction (XRD) pattern exposed that all coated films are tetragonal structure. And a peak shift was recorded after doping Ce ion into the V2O5 system. FE-SEM images showed a smooth nanorods and nanoplate-like structures in nano-scale region. Topology view by AFM showed a significant decrease in surface roughness of the film at different wt.% of Ce. The incorporation of Ce concentration based on the optical absorbance and band gap energy were studied, using UV–vis spectroscopy. Current-voltage (I–V), characteristics, photo-diode parameters of the Cu/Ce-V2O5/n-Si diodes were evaluated under dark and light exposed conditions. A maximum quantum efficiency of 25.54 % was achieved for the MIS diode fabricated with 6 % of Ce. The photosensitivity of the Cu/Ce-V2O5/n-Si diode 100 times higher than pure diode. Photodiode parameters and I–V analysis revealed that Ce with 6 wt.% is appropriate for the development of high quality photodiode and photo detector applications based to its electrical-performance.