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In this paper, S-doped vanadium oxide thin films with doping levels up to 40 at.% are prepared via spray pyrolysis method on glass substrates, and the effect of S-doping on the structural and photoconductivity related properties of β-V2O5 thin films is studied. The results show that most of the films have been grown in the tetragonal β-V2O5 phase structure with the preferred orientation along [200]. With increasing the doping level, the samples tend to be amorphous. The structure of the samples reveals to be nanobelt-shaped whose width decreases from nearly 100 nm to 40 nm with S concentration. The photoconductivity measurements show that by increasing the S-doping level, the photosensitivity increases, which is due to the prolonged electron’s lifetime as a result of enhanced defect states acting as trap levels.