Nanostructured hematite materials for advanced applications are conventionally prepared with the presence of additives, tainting its purity with remnants of copolymer surfactants, active chelating molecules, stabilizing agents, or co-precipitating salts. Thus, preparing nanostructured hematite via additive-free and green synthesis methods remains a huge hurdle. This study presents an environmentally friendly and facile synthesis of spherical nanostructured hematite (Sp-HNP) using rice starch-assisted synthesis. The physicochemical properties of the Sp-HNP were investigated by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DR UV-Vis), and nitrogen adsorption–desorption analysis. The Sp-HNP showed a well-crystallized structure of pure rhombohedral phase, having a spherical-shaped morphology from 24 to 48 nm, and a surface area of 20.04 m2/g. Moreover, the Sp-HNP exhibited enhanced photocatalytic degradation of methylene blue dye, owing to the large surface-to-volume ratio. The current work has provided a sustainable synthesis route to produce spherical nanostructured hematite without the use of any hazardous agents or toxic additives, in agreement with the principles of green chemistry for the degradation of dye contaminant.