Nanostructured hematite thin film for photoelectrochemical (PEC) splitting of water has great potential in the design of low-cost, environmental friendly solar-hydrogen production. Presently, solar-to-hydrogen conversion efficiency of PEC cell using iron oxide is limited by its poor charge transport due to high recombination losses and mismatch of band edges position with the redox level of water. High energy heavy ion irradiation provides the researchers a new dimension to introduce the desired changes in the behaviour of the material, which largely influence their properties. In order to get efficient PEC system, spray-pyrolytically deposited nanostructured hematite thin films were modified by irradiating the samples with 120 MeV Ag9+ ions with fluences ranging from 5×1011 to 1×1013 ions/cm2. Irradiated samples exhibited a partial transition from the hematite to the magnetite phase and reduction in particle size as indicated by XRD and Raman analysis. SEM picture showed a decrease the thickness and porosity of the films after irradiation. These irradiated films, when used in PEC cell showed significantly higher photocurrent density than unirradiated α-Fe2O3.