In this paper, Ce4+ and Fe3+co-doped titanium dioxide nanocomposite was prepared by iron nitrate, cerium sulfate and titanium sulfate as raw materials and sodium dodecyl sulfate as surfactant under microwave irradiation. The x-ray diffraction (XRD) results show that as-prepared sample of direct adding doped cerium and iron content were 0.2% and 0.5% of titanium sulfate amount of substance calcined at 500°C for 2 h is anatase. We also studied the photocatalytic activity of the as-prepared Fe3+ and Ce4+ co-doped TiO2 nanocomposite by using degradation of methyl orange solution. The effect conditions of photo-catalytic activities of the composite were investigated, such as different ratios of direct adding doped iron and cerium content, different dosage of hydrogen peroxide, different pH value, and different dosage of nanocomposite. When the catalyst is 1.0 g/L, pH value is 4.3, C(H2O2) is 3 mL/L, the effect of the visible light catalytic activity was the best, in 20 min, the degradation rate of 20 mg/L methyl orange solution was more than 90%. Obviously, as-prepared Fe3+ and Ce4+ co-doped titanium dioxide nanocomposite as photocatalysts for degradation methyl orange, has a significant effect. Moreover, the operation was simple, and there was no secondary pollution. In a word, it has a good prospect.