A simple and a novel chemical approach was used for the growth of α-Fe2O3 nanostructures. Field emission scanning electron microscopy analysis revealed the monodisperse nanoellipsoid morphology of α-Fe2O3 nanostructures. The sizes of the short axis and the long axis of these ellipsoids were in the ranges of 50–60 nm and 40–50 nm, respectively. XRD analysis revealed that the product exhibited α-Fe2O3 phase. Comprehensive TEM and HRTEM analysis revealed that α-Fe2O3 nanoellipsoids are single crystal in nature. The methylene blue decomposition kinetics was studied for different irradiation time. The methylene blue was totally decomposed by increasing the irradiation time up to 220 min.