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A photocatalytic, superhydrophilic, transparent, porous TiO2 film consisting of rice-shaped nano/mesostructures deposited on glass substrates by electrospinning has been developed. Optical properties such as transmittance and absorbance, as well as the superhydrophilicity and self-cleaning properties (photocatalysis) of the deposited TiO2 film are studied. The water contact angle decreases with increase in the thickness of the TiO2 resulting in superhydrophilic transparent coatings which may be used for applications in window coatings and photovoltaic modules. The self-cleaning property of the TiO2 film consisting of rice-shaped nano/mesostructures is compared with that of commercially available Degussa P-25 in the photodegradation of Alizarin red dye and found to be more effective.