Abstract: A simple and novel technique for the preparation of anatase TiO₂ nanopowders using natural ilmenite (FeTiO₃) as the starting material is reported. Digesting ilmenite with concentrated H₃PO₄ under refluxing conditions yields a white α-titanium bismonohydrogen orthophosphate monohydrate (TOP), Ti(HPO₄)₂·H₂O, which can be easily isolated via gravity separation from unreacted ilmenite. The addition of ammonia to the separated TOP followed by calcination at 500°C completes the preparation of anatase TiO₂. Calcination at temperatures above 800°C converts the anatase form of TiO₂ to the stable rutile phase. The removal of iron from ilmenite during the commercial production of synthetic TiO₂ is problematic and environmentally unfriendly. In the present study, the removal of iron was found to be markedly simple due to the high solubility of iron phosphate species in concentrated H₃PO₄ with the precipitation of TOP. The titanium content of the prepared samples on metal basis with silica and phosphorous as major impurities was over 90%. Prepared TiO₂ samples were characterized using X-ray fluorescence, Fourier-transform infrared spectroscopy, Raman spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, and X-ray diffraction analyses. The photocatalytic potentials of the commercial and as-prepared TiO₂ samples were assessed by the photodegradation of rhodamine B dye.