Iron(III) oxide (hematite, Fe2O3) nanofibers, as visible light-induced photoanode for water oxidation reaction of a water splitting process, were fabricated through electrospinning method followed by calcination treatment. The prepared samples were characterized with scanning electron microscopy, and three-electrode galvanostat/potentiostat for evaluating their photoelectrochemical (PEC) properties. The diameter of the as-spun fibers is about 300nm, and calcinated fibers have diameter less than 110nm with mesoporous structure. Optimized multilayered electrospun -Fe2O3 nanostructure mats showed photocurrent density of 0.53mA/cm(2) under dark and visible illumination conditions at voltage 1.23V and constant intensity (900mW/cm(2)). This photovoltaic performance of nanostructure mats makes it suitable choice for using in the PEC water splitting application as an efficient photoanode. This method, if combined with appropriate flexible conductive substrate, has the potential for producing flexible hematite solar fuel generators. Copyright (c) 2015 John Wiley & Sons, Ltd.