Abstract. In this work, Bi2O3 was deposited as a thin film of different thickness (400, 500, and 600 ±20 nm) by using thermal oxidation at 573 K with ambient oxygen of evaporated bismuth (Bi) thin films in a vacuum on glass substrate and on Si wafer to produce n-Bi2O3/p-Si heterojunction. The effect of thickness on the structural, electrical, surface and optical properties of Bi2O3 thin films was studied. XRD analysis reveals that all the as deposited Bi2O3 films show polycrystalline tetragonal structure, with preferential orientation in the (201) direction, without any change in structure due to increase of film thickness. AFM and SEM images are used to investigate the influences of film thickness on surface properties. The optical measurement were taken for the wave length range (400-1100) nm showed that the nature of the optical transition has been direct allowed with average band gap energies varies in the range of (2.9-2.25) eV with change thickness parameter. The extent and nature of transmittance, absorbance, reflectance and optimized band gap of the material assure to utilize it for photovoltaic applications. Hall measurements showed that all the films are n-type. The electrical properties of n-Bi2O3/p-Si heterojunction (HJ) were obtained by I-V (dark and illuminated) and C-V measurement at frequency (10 MHz) at different thickness. The ideality factor saturation current density, depletion width, built-in potential and carrier concentration are characterized under different thickness. The results show these HJ were of abrupt type. The photovoltaic measurements short-circuit current density, open-circuit voltage, fill factor and efficiencies are determined for all samples. Finally thermal oxidation allowed fabrication n-Bi2O3/p-Si heterojunction with different thickness for solar cell application.