TiO2 production is a key part of Ti metallurgy and Ti recycling, and the process itself has turned out to be energy-consuming and material-consuming. New technologies are needed to utilize complex Ti ores, such as ilmenite, and reduce the carbon footprint of TiO2 extraction. Ammonium sulfate roasting has been revealed as an efficient way to carry out phase transformations of complex minerals. A low-temperature sulfation roasting approach was studied to chemically breaking down the crystal structure of ilmenite and generate metal soluble sulfates simultaneously. These roasted products were introduced to water leaching, then the residue of the water leaching was leached by diluted HCl acid, and the TiO2 product was enriched in the leaching residue. The effects of roasting temperature, roasting time, ilmenite-to-ammonium sulfate mass ratio, ilmenite particle size, and second-stage roasting on iron removal and titanium loss leaching efficiency were systematically studied. The results show that the optimum roasting conditions were a roasting temperature of 500 °C, a roasting time of 210 min, an ilmenite-to-(NH4)2SO4 mass ratio of 1:7, and an ilmenite particle size of below 43 µm. Under optimized conditions, the TiO2 grade in the obtained synthetic rutile reached 75.83 wt.%. Furthermore, the phase transformation and reaction mechanism during roasting are discussed and interpreted.