The optical properties of the highly-textured V2O5 thin-films grown on Si(100) by sputter-deposition at various oxygen reactive-pressures were investigated in detail. The profiles of the optical constants, namely the refractive index and extinction coefficient, of V2O5 films were evaluated in the photon-energy range of 1–5 eV. At photon-energy above 2.5 eV, the dispersion behavior in optical constants is explained based on Lorentz-Drude model. The refractive index dispersion fits to a Cauchy’s relation at photon-energy below 2.5 eV, where the V2O5-film is mostly transparent. The optical transitions across the bandgap occur at energy ∼2.5–3.2 eV depending on the V2O5 growth conditions and film-microstructure. The highly-textured and c-axis oriented V2O5-films, fabricated under optimum conditions of temperature and oxygen partial pressure, exhibit excellent optical characteristics similar to V2O5 single crystals.