Vanadium oxide (VOx) has demonstrated significant potential in various applications, including sensors (included but not limited to photodetection), smart windows, and energy storage devices, attributed to its pronounced semiconductor-to-metal transition near 340 K, coupled with a structural transition.However, the requirement for high-temperature synthesis to achieve the desired phases for these applications has limited its broader utilization, particularly in contexts where high temperatures are impractical.Here, we examined the effect of thermal annealing on the structural, electronic, and photodetection properties of VOx/p-Si heterojunctions fabricated via dip coating.VOx films were categorized into three types: pristine (VOx-1), annealed at 300 °C (VOx-2), and 500 °C (VOx-3).X-ray diffraction anal. confirmed hydrated V2O5 in VO1-x and VOx-2, while VOx-3 was pure and crystalline V2O5.Significantly, the band gap narrowed from 2.75 eV in VOx-1 to 2.46 eV in VOx-3, a result attributed to grain growth and the consequential attenuation of quantum confinement effects.The DFT calculations implemented through the VASP code supported these findings, revealing an annealing-induced increase in the work function, revealing enhanced surface electronic properties favorable to photodetection.The elec. properties of the PN heterojunction Ag/n-VOx/p-Si/Ag with Ag/n-VOx terminal grounded showed a transition from ohmic-like in VOx-1 to rectifying behavior for VOx-2 and VOx-3 with dark condition reverse bias current larger than the forward bias current, showing typical Schottky junction type contact between p-Si and n-VOx.This behavior highlights the role of annealing in modulating the interface properties between p-Si and n-VOx.Notably, the heterojunctions demonstrated superior photodetection across IR, red, green, blue, and UV spectra, with performance metrics like responsivity and sensitivity markedly improved post-annealing, attributed to increased crystallinity and reduced interface traps and work function tuning.Addnl., the devices exhibited rapid transient responses under periodic LED illumination, highlighting their potential for advanced photodetection applications.