Ce4+-doped nanometer ZnO powder was synthesized by so-l gel method. The microstructures and properties of the samples were characterized through XRD, UV-Vis and FTIR. The results indicated that the Ce4+ was successfully incorporated into ZnO, and the diameter of the nanometer was about 10.7nm. It induced the redshifting in the UV-Vis spectra. The photocatalytic activity of the samples was investigated using methylene blue (MB) as the model reaction under irradiation with ultraviolet light. The results showed that the doping of Ce4+ could increase the photocatalytic activities of ZnO nanopowders and that the best molar ratio of Ce4+ was n(Ce)/n(Zn) = 0.05, that the surfactant was sodium dodecyl sulfate, and that the nanometer ZnO was calcinated at 550 ℃ for 3 hours. Meanwhile, it inspected the effect of photocatalytic efficiency through the pH of MB, the amount of catalyst, and illumination time. The experimental results revealed that the initial mass concentration of MB was 10 mg/L, that the pH value was 7-8, that the dosage of Ce4+/ZnO photo-catalyst was 5 g/L, that the UV-irradiation time was 2 h, and that the removal rate of MB reached above 85%. Under the optimized conditions, the degradation rate of real dye wastewater was up to 87.67% and the removal efficiency of COD was 63.5%.