The paper preliminary studied the photocatalytic efficiency of the filter residue of the acidolysis of high titanium slag (RAHTS) with hydrochloric acid, and explored the photocatalytic efficiency on the acid methyl orange solution under the mercury lamp irradiation. With RAHTS performing as a raw material to react with hydrochloric acid, and then the substance content, nature and catalytic efficiency of the filter residues were examined by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and photocatalytic reaction apparatus. Through the experimental investigation, the photocatalytic degradation efficiency on the methyl orange of the filter residues increased with the acid-sludge ratio, reaction time, reaction temperature, and the concentration of hydrochloric acid. When the temperature was 100°C, the reaction time was 4 h, the concentration of the hydrochloric acid was 6 mol/L, the acid-sludge ratio was 1, the filter residues showed a best photocatalytic degradation efficiency. Under that experimental condition, the degradation rate was as high as 85.1%.