Hematite (alpha-Fe2O3) is a promising photoanode material for hydrogen production from photo-electrochemical (PEC) water splitting due to its wide abundance, narrow band-gap energy, efficient light absorption and high chemical stability under aqueous environment. The key challenge to the wider utilisation of nanostructured hematite-based photoanode in PEC water splitting, however, is limited by its low photo-assisted water oxidation caused by large overpotential in the nominal range of 0.5-0.6 V. The main aim of this study was to enhance the performance of hematite for photo-assisted water oxidation by optimising the annealing temperature used during the synthesis of nanostructured hematite thin films on fluorine-doped tin oxide (FTO)-based photoanodes prepared via the cathodic electrodeposition method. The resultant nanostructured hematite thin films were characterised using field emission-scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) for their elemental composition, average nanocrystallites size and morphology; phase and crystallinity; UV-absorptivity and band gap energy; and the functional groups, respectively. Results showed that the nanostructured hematite thin films possess good ordered nanocrystallites array and high crystallinity after annealing treatment at 400-600 degrees C. FE-SEM images illustrated an increase in the average hematite nanocrystallites size from 65 nm to 95 nm when the annealing temperature was varied from 400 degrees C to 600 degrees C. As the crystallites size increases, the grain boundaries reduce and this suppresses the recombination rate of electron-hole pairs on the nanostructured hematite thin films. As a result, the measured photocurrent densities of nanostructured hematite thin films also increased. The highest measured photocurrent density of 1.6 mA/cm(2) at 0.6 V vs Ag/AgCl in 1 M NaOH electrolyte was achieved for the nanostructured hematite thin film annealed at 600 degrees C. This study had confirmed that strong interdependencies exist between the average hematite nanocrystallites size and grain boundaries with annealing temperature on the eventual PEC water splitting performance of nanostructured hematite thin films. The annealed hematite thin films at a higher temperature will enhance the nanocrystals growth and thus, suppressing the electron-hole pairs recombination rate, lowering the grain boundary resistance and enabling higher photocurrent flow at the molecular level. As a result, the photocurrent density and thus, the overall PEC water splitting performance of the nanostructured hematite thin films are significantly enhanced. (C) 2014 Elsevier Ltd. All rights reserved.