The ferrous ion content of metatitanic acid affected the whiteness, purity and applications of TiO2, controlled by the hydrolysis conditions and metatitanic acid structure. The structural evolution of metatitanic acid and ferrous ion removal was investigated by hydrolyzing the industrial TiOSO4solution. The hydrolysis degree was conformed to Boltzmann model with good fitting. TiO2content of metatitanic acid gradually increased as hydrolysis proceeding due to its stronger compact structure and weaker colloidal property, caused by the aggregation and adjustment of the precipitated particles. At lower TiOSO4concentration, the crystal size increased significantly, lattice strain decreased, and average particle size constantly adjusted and reduced. The micropores and mesopores were mainly formed by aggregating and stacking of primary agglomerate particles, bonded and filled with sulfate and hydroxyl. The ferrous ion content decreased linearly with the increase of TiO2content, and reducing moisture content of metatitanic acid was an effective way to reduce Fe content. This would save more water and energy consumption, help to improve the clean production level of TiO2.