In this study, a rapid and efficient method of recovering TiO₂ from spent SCR (selective catalytic reduction) catalyst supplied by a coal-fired power plant in Shanghai was developed. The acid leaching and sodium roasting-water leaching residues (titanium slag) from spent SCR catalyst were employed as the raw material. First, titanium slag was dissolved into H₂SO₄ solution under different conditions. The optimal acidolysis conditions were 85 wt% H₂SO₄, 5.0 g/g acid-residues ratio, 90℃ acidolysis temperature and 2.0 h acidolysis time. Simultaneously, the highest acidolysis efficiency can reach 92.02%. The acidolysis solution was collected and concentrated to 200 g/L (measured by TiO₂ concentration). Then, acidolysis solution was adjusted to pH 0.52-9.15, followed by adding 0-40 mL additional crystal seeds and reacting under certain conditions to obtain the hydrolysis product. The optimal hydrolysis conditions were 25 mL additional crystal seeds, pH 7.46, 120℃ hydrolysis temperature and 3.0 h hydrolysis time. Finally, the recovered product was obtained by roasting hydrolysis product at 700℃ for 2.0 h. The results of hydrolysis stability test indicated that this method can make the hydrolysis efficiency of acidolysis solution stabilize at approximately 90% under optimal conditions. The main component of recovered product was anatase TiO₂ with the purity of 86.88%.