A simple and novel technique for the preparation of anatase TiO2 nanopowders using natural ilmenite (FeTiO3) as the starting mater-ial is reported. Digesting ilmenite with concentrated H3PO4 under refluxing conditions yields a white α-titanium bismonohydrogen orthophos-phate monohydrate (TOP), Ti(HPO4)2·H2O, which can be easily isolated via gravity separation from unreacted ilmenite. The addition of am-monia 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 syn-thetic 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 fluores-cence, 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.